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Acid--Base Equilibria

Acid

Hoa Dai Cuong A2

Chapter 3

Acids and Bases


Bases::
Acid: v chua, lm thuc nhum i mu
Bases: v ng, cm gic nht.
Arrhenius: acids lm tng [H+], bases lm tng
[OH-] trong dung dch.
Arrhenius: acid + base salt + water.
Problem: nh ngha ny ch p dng c
trong dung dch nc

Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
The H+ Ion in Water
The H+(aq) ion is simply a proton with no
electrons. (H has one proton, one electron, and
no neutrons.)
In water, the H+(aq) form clusters.
The simplest cluster is H3O+(aq).
Larger
clusters are H5O2+ and H9O4+.
Generally we use H+(aq) and H3O+(aq)
interchangeably.

Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
The H+ Ion in Water

Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
Proton Transfer Reactions
Focus on the H+(aq).
Brnsted-Lowry: acid donates H+ and base accepts H+.
Brnsted-Lowry base does not need to contain OH-.
Consider HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq):
HCl donates a proton to water. Therefore, HCl is an
acid.
H2O accepts a proton from HCl. Therefore, H2O is a
base.
Water can behave as either an acid or a base.
Amphoteric substances can behave as acids and
bases.
Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
Proton Transfer Reactions

Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
Conjugate AcidAcid-Base Pairs
Whatever is left of the acid after the proton is donated
is called its conjugate base.
Similarly, whatever remains of the base after it accepts
a proton is called a conjugate acid.
Consider HA(aq) + H2O(l)
H3O+(aq) + A-(aq)
After HA (acid) loses its proton it is converted into
A- (base). Therefore HA and A- are conjugate acidbase pairs.
After H2O (base) gains a proton it is converted into
H3O+ (acid). Therefore, H2O and H3O+ are conjugate
acid-base pairs.
Conjugate acid-base pairs differ by only one proton.
Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
Relative Strengths of Acids
and Bases
The stronger the acid, the
weaker the conjugate base.
H+ is the strongest acid that
can exist in equilibrium in
aqueous solution.
OH- is the strongest base
that can exist in equilibrium
in aqueous solution.

Hoa Dai Cuong A2

Chapter 3

Brnsted--Lowry Acids and Bases


Brnsted
Relative Strengths of Acids and Bases
Any acid or base that is stronger than H+ or OHsimply reacts stoichiometrically to produce H+
and OH-.
The conjugate base of a strong acid (e.g. Cl-)
has negligible acid-base properties.
Similarly, the conjugate acid of a strong base
has negligible acid-base properties.

Hoa Dai Cuong A2

Chapter 3

The Autoionization of Water


The Ion Product of Water
In pure water the following equilibrium is
established

H3O+(aq) + OH-(aq)

H2O(l) + H2O(l)
at 25 C

Kc =

[H 3O + ][OH - ]
[H 2O]2

K c [H 2O]2 = [H 3O + ][OH - ]
K w = [H 3O + ][OH - ] = 1.0 1014
The above is called the autoionization of water.
Hoa Dai Cuong A2

Chapter 3

10

The pH Scale
In most solutions [H+(aq)] is quite small.
We define pH = -log[H+] = -log[H3O+]. Similarly
pOH = -log[OH-].
In neutral water at 25 C, pH = pOH = 7.00.
In acidic solutions, [H+] > 1.0 10-7, so pH < 7.00.
In basic solutions, [H+] < 1.0 10-7, so pH > 7.00.
The higher the pH, the lower the pOH, the more
basic the solution.
Most pH and pOH values fall between 0 and 14.
There are no theoretical limits on the values of
pH or pOH. (e.g. pH of 2.0 M HCl is -0.301)
Hoa Dai Cuong A2

Chapter 3

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Chapter 3

12

The pH Scale

Hoa Dai Cuong A2

The pH Scale
Other p Scales
In general for a number X,

pX = log X

For example, pKw = -log Kw.


Since
K w = [H 3O + ][OH - ] = 1.0 1014
pK w = log [H 3O + ][OH - ] = 14.00
log[H 3O + ] log[OH - ] = 14.00
pH + pOH = 14.00

Hoa Dai Cuong A2

Chapter 3

13

The pH Scale
Measuring pH
Most accurate method to measure pH is to use a
pH meter.
However, certain dyes change color as pH
changes. These are indicators.
Indicators are less precise than pH meters.
Many indicators do not have a sharp color
change as a function of pH.
Most indicators tend to be red in more acidic
solutions (two exceptions: phenolphthalein and
alizarin yellow R are both red in base).
Hoa Dai Cuong A2

Chapter 3

14

The pH Scale
Measuring pH

Hoa Dai Cuong A2

Chapter 3

15

Strong Acids and Bases


Strong Acids
The strongest common acids are HCl, HBr, HI,
HNO3, HClO3, HClO4, and H2SO4.
Strong acids are strong electrolytes.
All strong acids ionize completely in solution:
HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq)
Since H+ and H3O+ are used interchangeably, we
write
HNO3(aq) H+(aq) + NO3-(aq)

Hoa Dai Cuong A2

Chapter 3

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Strong Acids and Bases


Strong Acids
In solutions the strong acid is usually the only
source of H+. (If the molarity of the acid is less
than 10-6 M then the autoionization of water
needs to be taken into account.)
Therefore, the pH of the solution is the initial
molarity of the acid.
Strong Bases
Most ionic hydroxides are strong bases (e.g.
NaOH, KOH, and Ca(OH)2).

Hoa Dai Cuong A2

Chapter 3

17

Strong Acids and Bases


Strong Bases
Strong bases are strong electrolytes and
dissociate completely in solution.
The pOH (and hence pH) of a strong base is
given by the initial molarity of the base. Be
careful of stoichiometry.
In order for a hydroxide to be a base, it must be
soluble.
Bases do not have to contain the OH- ion:
O2-(aq) + H2O(l) 2OH-(aq)
H-(aq) + H2O(l) H2(g) + OH-(aq)
N3-(aq) + H2O(l) NH3(aq) + 3OH-(aq)
Hoa Dai Cuong A2

Chapter 3

18

Weak Acids
Weak acids are only partially ionized in solution.
There is a mixture of ions and unionized acid in
solution.
Therefore, weak acids are in equilibrium:

H3O+(aq) + A-(aq)

HA(aq) + H2O(l)
HA(aq)
[H 3O + ][A - ]
Ka =
[HA]

H+(aq) + A-(aq)
or

[H + ][A - ]
Ka =
[HA]

Ka is the acid dissociation constant.


Hoa Dai Cuong A2

Chapter 3

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Chapter 3

20

Weak Acids

Hoa Dai Cuong A2

Weak Acids
Note [H2O] is omitted from the Ka expression.
(H2O is a pure liquid.)
The larger the Ka the stronger the acid (i.e. the
more ions are present at equilibrium relative to
unionized molecules).
If Ka >> 1, then the acid is completely ionized
and the acid is a strong acid.

Using Ka to Calculate pH
Weak acids are simply equilibrium calculations.
The pH gives the equilibrium concentration of
H+.
Hoa Dai Cuong A2

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Weak Acids
Using Ka to Calculate pH
Using Ka, the concentration of H+ (and hence the
pH) can be calculated.
Write the balanced chemical equation clearly showing
the equilibrium.
Write the equilibrium expression. Find the value for
Ka.
Write down the initial and equilibrium concentrations
for everything except pure water. We usually assume
that the change in concentration of H+ is x.

Substitute into the equilibrium constant


expression and solve. Remember to turn x into
pH if necessary.
Hoa Dai Cuong A2

Chapter 3

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Weak Acids
Using Ka to Calculate pH
Percent ionization is another method to assess
acid strength.
For the reaction

H3O+(aq) + A-(aq)
[H + ]eqm
% ionization =
100
[HA ]0

HA(aq) + H2O(l)

Percent ionization relates the equilibrium H+


concentration, [H+]eqm, to the initial HA
concentration, [HA]0.
Hoa Dai Cuong A2

Chapter 3

23

Weak Acids
Using Ka to Calculate pH
The higher percent ionization, the stronger the
acid.
Percent ionization of a weak acid decreases as
the molarity of the solution increases.
For acetic acid, 0.05 M solution is 2.0 % ionized
whereas a 0.15 M solution is 1.0 % ionized.

Hoa Dai Cuong A2

Chapter 3

24

Weak Acids
Using Ka to Calculate pH

Hoa Dai Cuong A2

Chapter 3

25

Weak Acids
Polyprotic Acids
Polyprotic acids have more than one ionizable
proton.
The protons are removed in steps not all at once:

H2SO3(aq)

H+(aq) + HSO3-(aq) Ka1 = 1.7 x 10-2

HSO3-(aq)

H+(aq) + SO32-(aq)

Ka2 = 6.4 x 10-8

It is always easier to remove the first proton in a


polyprotic acid than the second.
Therefore, Ka1 > Ka2 > Ka3 etc.
Most H+(aq) at equilibrium usually comes from the
first ionization (i.e. the Ka1 equilibrium).
Hoa Dai Cuong A2

Chapter 3

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Weak Acids
Polyprotic Acids

Hoa Dai Cuong A2

Chapter 3

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Weak Bases
Weak bases remove protons from substances.
There is an equilibrium between the base and
the resulting ions:
Weak base + H2O

conjugate acid + OH-

Example:
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq)
The base dissociation constant, Kb, is defined
as
[NH 4+ ][OH - ]
Kb =
[NH 3 ]

Hoa Dai Cuong A2

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Weak Bases
The larger Kb the stronger the base.

Hoa Dai Cuong A2

Chapter 3

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Weak Bases
Types of Weak Bases
Bases generally have lone pairs or negative
charges in order to attack protons.
Most neutral weak bases contain nitrogen.
Amines are related to ammonia and have one or
more N-H bonds replaced with N-C bonds (e.g.,
CH3NH2 is methylamine).
Anions of weak acids are also weak bases.
Example: OCl- is the conjugate base of HOCl
(weak acid):
ClO-(aq) + H2O(l)
Hoa Dai Cuong A2

HClO(aq) + OH-(aq) Kb = 3.3 x 10-7


Chapter 3

30

Relationship Between Ka and Kb


We need to quantify the relationship between
strength of acid and conjugate base.
When two reactions are added to give a third,
the equilibrium constant for the third reaction is
the product of the equilibrium constants for the
first two:
Reaction 1 + reaction 2 = reaction 3
has
K1 K2 = K3.

Hoa Dai Cuong A2

Chapter 3

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Relationship Between Ka and Kb


For a conjugate acid-base pair
Ka Kb = Kw
Therefore, the larger the Ka, the smaller the Kb.
That is, the stronger the acid, the weaker the
conjugate base.
Taking negative logarithms:
pKa + pKb = pKw

Hoa Dai Cuong A2

Chapter 3

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Acid--Base Properties of Salt Solutions


Acid
Nearly all salts are strong electrolytes.
Therefore, salts exist entirely of ions in solution.
Acid-base properties of salts are a consequence
of the reaction of their ions in solution.
The reaction in which ions produce H+ or OH- in
water is called hydrolysis.
Anions from weak acids are basic.
Anions from strong acids are neutral.
Anions with ionizable protons (e.g. HSO4-) are
amphoteric.

Hoa Dai Cuong A2

Chapter 3

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Acid--Base Properties of Salt Solutions


Acid
To determine whether a salt has acid-base
properties we use:
Salts derived from a strong acid and strong base are
neutral (e.g. NaCl, Ca(NO3)2).
Salts derived from a strong base and weak acid are
basic (e.g. NaOCl, Ba(C2H3O2)2).
Salts derived from a weak base and strong base are
acidic (e.g. NH4Cl, Al(NO3)3).
Salts derived from a weak acid and weak base can be
either acidic or basic. Equilibrium rules apply!

Hoa Dai Cuong A2

Chapter 3

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Acid--Base Behavior and Chemical Structure


Acid
Factors That Affect Acid Strength
Consider H-X. For this substance to be an acid we
need:
H-X bond to be polar with H
+ and X
- (if X is a
metal then the bond polarity is H
-, X
+ and the
substance is a base),
the H-X bond must be weak enough to be
broken,
the conjugate base, X-, must be stable.

Hoa Dai Cuong A2

Chapter 3

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Acid--Base Behavior and Chemical Structure


Acid
Binary Acids
Acid strength increases across a period and
down a group.
Conversely, base strength decreases across a
period and down a group.
HF is a weak acid because the bond energy is
high.
The electronegativity difference between C and
H is so small that the C-H bond is non-polar and
CH4 is neither an acid nor a base.
Hoa Dai Cuong A2

Chapter 3

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Acid-Base Behavior and Chemical


AcidStructure
Binary Acids

Hoa Dai Cuong A2

Chapter 3

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Acid--Base Behavior and Chemical Structure


Acid
Oxyacids
Oxyacids contain O-H bonds.
All oxyacids have the general structure Y-O-H.
The strength of the acid depends on Y and the
atoms attached to Y.
If Y is a metal (low electronegativity), then the
substances are bases.
If Y has intermediate electronegativity (e.g. I, EN =
2.5), the electrons are between Y and O and the
substance is a weak oxyacid.

Hoa Dai Cuong A2

Chapter 3

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Acid--Base Behavior and Chemical Structure


Acid
Oxyacids
If Y has a large electronegativity (e.g. Cl, EN =
3.0), the electrons are located closer to Y than
O and the O-H bond is polarized to lose H+.
The number of O atoms attached to Y
increase the O-H bond polarity and the
strength of the acid increases (e.g. HOCl is a
weaker acid than HClO2 which is weaker than
HClO3 which is weaker than HClO4 which is a
strong acid).
Hoa Dai Cuong A2

Chapter 3

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Acid-Base Behavior and Chemical


AcidStructure
Oxyacids

Hoa Dai Cuong A2

Chapter 3

40

Acid--Base Behavior and Chemical Structure


Acid
Carboxylic Acids
These are organic acids which contain a COOH
group (R is some carbon containing unit):

O
R

Hoa Dai Cuong A2

OH

Chapter 3

41

Acid--Base Behavior and Chemical Structure


Acid
Carboxylic Acids
When the proton is removed, the negative
charge is delocalized over the carboxylate
anion:
O
O
R

The acid strength increases as the number of


electronegative groups on R increases.
Hoa Dai Cuong A2

Chapter 3

42

Lewis Acids and Bases


Brnsted-Lowry acid is a proton donor.
Focusing on electrons: a Brnsted-Lowry acid
can be considered as an electron pair acceptor.
Lewis acid: electron pair acceptor.
Lewis base: electron pair donor.
Note: Lewis acids and bases do not need to
contain protons.
Therefore, the Lewis definition is the most
general definition of acids and bases.

Hoa Dai Cuong A2

Chapter 3

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Lewis Acids and Bases


Lewis acids generally have an incomplete octet
(e.g. BF3).
Transition metal ions are generally Lewis acids.
Lewis acids must have a vacant orbital (into
which the electron pairs can be donated).
Compounds with p-bonds can act as Lewis
acids:
H2O(l) + CO2(g) H2CO3(aq)

Hoa Dai Cuong A2

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Lewis Acids and Bases


Hydrolysis of Metal Ions
Metal ions are positively charged and attract
water molecules (via the lone pairs on O).
The higher the charge, the smaller the metal ion
and the stronger the M-OH2 interaction.
Hydrated metal ions act as acids:
Fe(H2O)63+(aq)

Fe(H2O)5(OH)2+(aq) + H+(aq) Ka = 2 x 10-3

The pH increases as the size of the ion


increases (e.g. Ca2+ vs. Zn2+) and as the charge
increases (Na+ vs. Ca2+ and Zn2+ vs. Al3+).

Hoa Dai Cuong A2

Chapter 3

45

Additional Aspects of
Aqueous Equilibria
David P. White
University of North Carolina, Wilmington
Chapter 17
Copyright 1999, PRENTICE HALL

Chapter 17

The Common Ion Effect


The solubility of a partially soluble salt is decreased
when a common ion is added.
Consider the equilibrium established when acetic
acid, HC2H3O2, is added to water.
At equilibrium H+ and C2H3O2- are constantly moving
into and out of solution, but the concentrations of ions
is constant and equal.
If a common ion is added, e.g. C2H3O2- from
NaC2H3O2 (which is a strong electrolyte) then
[C2H3O2-] increases and the system is no longer at
equilibrium.
So, [H+] must decrease.
Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Composition and Action of Buffered Solutions
A buffer consists of a mixture of a weak acid (HX)
and its conjugate base (X-):

HX(aq)

H+(aq) + X-(aq)

The Ka expression is

[H + ][ X- ]
Ka =
.
[HX]
[HX]
[H + ] = K a
.
[X ]
A buffer resists a change in pH when a small amount
of OH- or H+ is added.
Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Composition and Action of Buffered Solutions
When OH- is added to the buffer, the OH- reacts with
HX to produce X- and water. But, the [HX]/[X-] ratio
remains more or less constant, so the pH is not
significantly changed.
When H+ is added to the buffer, X- is consumed to
produce HX. Once again, the [HX]/[X-] ratio is more
or less constant, so the pH does not change
significantly.

Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Composition and Action of Buffered Solutions

Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Buffer Capacity and pH
Buffer capacity is the amount of acid or base
neutralized by the buffer before there is a significant
change in pH.
Buffer capacity depends on the composition of the
buffer.
The greater the amounts of conjugate acid-base pair,
the greater the buffer capacity.
The pH of the buffer depends on Ka.

Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Buffer Capacity and pH
If Ka is small (i.e., if the equilibrium concentration of
undissociated acid is close to the initial
concentration), then
[HX]
[H + ] = K a
[X- ]

log[ H + ] = log K a log

[HX]
[ X- ]

[ X- ]
pH = p K a + log
.
[HX]
Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Addition of Strong Acids or Bases to Buffers
We break the calculation into two parts:
stoichiometric and equilibrium.
The amount of strong acid or base added results in a
neutralization reaction:
X- + H3O+ HX + H2O
HX + OH- X- + H2O.
By knowing how much H3O+ or OH- was added
(stoichiometry) we know how much HX or X- is
formed.

Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Addition of Strong Acids or Bases to Buffers

Copyright 1999, PRENTICE HALL

Chapter 17

Buffered Solutions
Addition of Strong Acids or Bases to Buffers
With the concentrations of HX and X- (note the
change in volume of solution) we can calculate the pH
from the Henderson-Hasselbalch equation

[ X- ]
pH = p K a + log
[HX]
conjugate base
pH = p K a + log
conjugate acid

Copyright 1999, PRENTICE HALL

Chapter 17

10

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations

The plot of pH
versus volume
during a titration
is a titration curve.

Copyright 1999, PRENTICE HALL

Chapter 17

11

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations
Consider adding a strong base (e.g. NaOH) to a
solution of a strong acid (e.g. HCl).
Before any base is added, the pH is given by the strong acid
solution. Therefore, pH < 7.
When base is added, before the equivalence point, the pH is
given by the amount of strong acid in excess. Therefore, pH
< 7.
At equivalence point, the amount of base added is
stoichiometrically equivalent to the amount of acid
originally present. Therefore, the pH is determined by the
salt solution. Therefore, pH = 7.
Copyright 1999, PRENTICE HALL

Chapter 17

12

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations
Consider adding a strong base (e.g. NaOH) to a
solution of a strong acid (e.g. HCl).

Copyright 1999, PRENTICE HALL

Chapter 17

13

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations
We know the pH at equivalent point is 7.00.
To detect the equivalent point, we use an indicator
that changes color somewhere near 7.00.
Usually, we use phenolphthalein that changes color between
pH 8.3 to 10.0.
In acid, phenolphthalein is colorless.
As NaOH is added, there is a slight pink color at the
addition point.
When the flask is swirled and the reagents mixed, the pink
color disappears.
At the end point, the solution is light pink.
If more base is added, the solution turns darker pink.
Copyright 1999, PRENTICE HALL

Chapter 17

14

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations
The equivalence point in a titration is the point at
which the acid and base are present in stoichiometric
quantities.
The end point in a titration is the observed point.
The difference between equivalence point and end
point is called the titration error.
The shape of a strong base-strong acid titration curve
is very similar to a strong acid-strong base titration
curve.

Copyright 1999, PRENTICE HALL

Chapter 17

15

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations

Copyright 1999, PRENTICE HALL

Chapter 17

16

Acid--Base Titrations
Acid
Strong AcidAcid-Base Titrations
Initially, the strong base is in excess, so the pH > 7.
As acid is added, the pH decreases but is still greater
than 7.
At equivalence point, the pH is given by the salt
solution (i.e. pH = 7).
After equivalence point, the pH is given by the strong
acid in excess, so pH < 7.

Copyright 1999, PRENTICE HALL

Chapter 17

17

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations
Consider the titration of acetic acid, HC2H3O2 and
NaOH.
Before any base is added, the solution contains only
weak acid. Therefore, pH is given by the equilibrium
calculation.
As strong base is added, the strong base consumes a
stoichiometric quantity of weak acid:
HC2H3O2(aq) + NaOH(aq) C2H3O2-(aq) + H2O(l)

Copyright 1999, PRENTICE HALL

Chapter 17

18

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations

Copyright 1999, PRENTICE HALL

Chapter 17

19

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations
There is an excess of acetic acid before the
equivalence point.
Therefore, we have a mixture of weak acid and its
conjugate base.
The pH is given by the buffer calculation.
First the amount of C2H3O2- generated is calculated, as well as the
amount of HC2H3O2 consumed. (Stoichiometry.)
Then the pH is calculated using equilibrium conditions. (HendersonHasselbalch.)

Copyright 1999, PRENTICE HALL

Chapter 17

20

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations
At the equivalence point, all the acetic acid has been
consumed and all the NaOH has been consumed.
However, C2H3O2- has been generated.
Therefore, the pH is given by the C2H3O2- solution.
This means pH > 7.
More importantly, pH 7 for a weak acid-strong base titration.

After the equivalence point, the pH is given by the


strong base in excess.

Copyright 1999, PRENTICE HALL

Chapter 17

21

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations
For a strong acid-strong base titration, the pH begins
at less than 7 and gradually increases as base is
added.
Near the equivalence point, the pH increases
dramatically.
For a weak acid-strong base titration, the initial pH
rise is more steep than the strong acid-strong base
case.
However, then there is a leveling off due to buffer
effects.
Copyright 1999, PRENTICE HALL

Chapter 17

22

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations
The inflection point is not as steep for a weak acidstrong base titration.
The shape of the two curves after equivalence point is
the same because pH is determined by the strong base
in excess.
Two features of titration curves are affected by the
strength of the acid:
the amount of the initial rise in pH, and
the length of the inflection point at equivalence.

Copyright 1999, PRENTICE HALL

Chapter 17

23

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations

The weaker the acid,


the smaller the
equivalence point
inflection.
For very weak acids, it
is impossible to detect
the equivalence point.

Copyright 1999, PRENTICE HALL

Chapter 17

24

Acid--Base Titrations
Acid
Weak AcidAcid-Strong Base Titrations
Titration of weak bases with strong acids have similar
features to weak acid-strong base titrations.

Copyright 1999, PRENTICE HALL

Chapter 17

25

Acid--Base Titrations
Acid
Titrations of Polyprotic Acids
In polyprotic acids, each ionizable proton dissociates
in steps.
Therefore, in a titration there are n equivalence points
corresponding to each ionizable proton.
In the titration of Na2CO3 with HCl there are two
equivalence points:
one for the formation of HCO3 one for the formation of H2CO3.

Copyright 1999, PRENTICE HALL

Chapter 17

26

Acid--Base Titrations
Acid
Titrations of Polyprotic Acids

Copyright 1999, PRENTICE HALL

Chapter 17

27

Solubility Equilibria
Solubility--Product Constant, Ksp
Solubility
Consider

BaSO4(s)

Ba2+(aq) + SO42-(aq)

for which

+ ][SO 2- ]
K sp = [Ba 2+
4
Ksp is the solubility product. (BaSO4 is ignored
because it is a pure solid so its concentration is
constant.)

Copyright 1999, PRENTICE HALL

Chapter 17

28

Solubility Equilibria
Solubility--Product Constant, Ksp
Solubility
In general: the solubility product is the molar
concentration of ions raised to their stoichiometric
powers.
Solubility is the amount (grams) of substance that
dissolves to form a saturated solution.
Molar solubility is the number of moles of solute
dissolving to form a liter of saturated solution.

Copyright 1999, PRENTICE HALL

Chapter 17

29

Solubility Equilibria
Solubility and Ksp
To convert solubility to Ksp
solubility needs to be converted into molar solubility
(via molar mass);
molar solubility is converted into the molar
concentration of ions at equilibrium (equilibrium
calculation),
Ksp is the product of equilibrium concentration of
ions.

Copyright 1999, PRENTICE HALL

Chapter 17

30

Solubility Equilibria
Solubility and Ksp

Copyright 1999, PRENTICE HALL

Chapter 17

31

Factors That Affect Solubility


Common--Ion Effect
Common
Solubility is decreased when a common ion is added.
This is an application of Le Chteliers principle:

CaF2(s)

Ca2+(aq) + 2F-(aq)

as F- (from NaF, say) is added, the equilibrium shifts


away from the increase.
Therefore, CaF2(s) is formed and precipitation occurs.
As NaF is added to the system, the solubility of CaF2
decreases.

Copyright 1999, PRENTICE HALL

Chapter 17

32

Factors That Affect Solubility


Common--Ion Effect
Common

Copyright 1999, PRENTICE HALL

Chapter 17

33

Factors That Affect Solubility


Solubility and pH
Again we apply Le Chteliers principle:

CaF2(s)

Ca2+(aq) + 2F-(aq)

If the F- is removed, then the equilibrium shifts towards the


decrease and CaF2 dissolves.
F- can be removed by adding a strong acid:
+

F (aq) + H (aq)

HF(aq)

As pH decreases, [H+] increases and solubility increases.

The effect of pH on solubility is dramatic.

Copyright 1999, PRENTICE HALL

Chapter 17

34

Factors That Affect Solubility


Solubility and pH

Copyright 1999, PRENTICE HALL

Chapter 17

35

Factors That Affect Solubility


Formation of Complex Ions
Consider the formation of Ag(NH3)2+:

Ag+(aq) + 2NH3(aq)

Ag(NH3)2(aq)

The Ag(NH3)2+ is called a complex ion.


NH3 (the attached Lewis base) is called a ligand.
The equilibrium constant for the reaction is called the
formation constant, Kf:
[ Ag(NH 3 )2 + ]
Kf =
.
2
+
[Ag ][NH 3 ]
Focus on Lewis acid-base chemistry and solubility.
Copyright 1999, PRENTICE HALL

Chapter 17

36

Factors That Affect Solubility


Formation of Complex Ions

Copyright 1999, PRENTICE HALL

Chapter 17

37

Factors That Affect Solubility


Formation of Complex Ions
Consider the addition of ammonia to AgCl (white
precipitate):

AgCl(s)

Ag+(aq) + Cl-(aq)

Ag+(aq) + 2NH3(aq)

Ag(NH3)2(aq)

The overall reaction is

AgCl(s) + 2NH3(aq)

Ag(NH3)2(aq) + Cl-(aq)

Effectively, the Ag+(aq) has been removed from


solution.
By Le Chteliers principle, the forward reaction (the
dissolving of AgCl) is favored.
Copyright 1999, PRENTICE HALL

Chapter 17

38

Factors That Affect Solubility


Amphoterism
Amphoteric oxides will dissolve in either a strong acid
or a strong base.
Examples: hydroxides and oxides of Al3+, Cr3+, Zn2+,
and Sn2+.
The hydroxides generally form complex ions with four
hydroxide ligands attached to the metal:

Al(OH3)(s) + OH-(aq)

Al(OH)4-(aq)

Hydrated metal ions act as weak acids. Thus, the


amphoterism is interrupted:

Copyright 1999, PRENTICE HALL

Chapter 17

39

Factors That Affect Solubility


Amphoterism
Hydrated metal ions act as weak acids. Thus, the
amphoterism is interrupted:
Al(H2O)63+(aq) + OH-(aq)

Al(H2O)5(OH)2+(aq) + H2O(l)

Al(H2O)5(OH)2+(aq) + OH-(aq)

Al(H2O)4(OH)+(aq) + OH-(aq)

Al(H2O)3(OH)3(s) + H2O(l)

Al(H2O)2(OH)4-(aq) + H2O(l)

Al(H2O)3(OH)3(s) + OH-(aq)

Copyright 1999, PRENTICE HALL

Al(H2O)4(OH)2+(aq) + H2O(l)

Chapter 17

40

Precipitation and Separation of Ions


BaSO4(s)

Ba2+(aq) + SO42-(aq)

At any instant in time, Q = [Ba2+][SO42-].


If Q < Ksp, precipitation occurs until Q = Ksp.
If Q = Ksp, equilibrium exists.
If Q > Ksp, solid dissolves until Q = Ksp.

Based on solubilities, ions can be selectively removed


from solutions.
Consider a mixture of Zn2+(aq) and Cu2+(aq). CuS
(Ksp = 6 10-37) is less soluble than ZnS (Ksp =
2
10-25), CuS will be removed from solution before ZnS.

Copyright 1999, PRENTICE HALL

Chapter 17

41

Precipitation and Separation of Ions


As H2S is added to the green solution, black CuS
forms in a colorless solution of Zn2+(aq).
When more H2S is added, a second precipitate of
white ZnS forms.

Selective Precipitation of Ions


Ions can be separated from each other based on their
salt solubilities.
Example: if HCl is added to a solution containing Ag+
and Cu2+, the silver precipitates (Ksp for AgCl is 1.8
10-10) while the Cu2+ remains in solution.
Removal of one metal ion from a solution is called
selective precipitation.
Copyright 1999, PRENTICE HALL

Chapter 17

42

Qualitative Analysis for Metallic Elements

Qualitative analysis is
designed to detect the
presence of metal ions.
Quantitative analysis is
designed to determine how
much metal ion is present.

Copyright 1999, PRENTICE HALL

Chapter 17

43

Qualitative Analysis for Metallic Elements


We can separate a complicated mixture of ions into
five groups:
Add 6 M HCl to precipitate insoluble chlorides (AgCl,
Hg2Cl2, and PbCl2).
To the remaining mix of cations, add H2S in 0.2 M HCl to
remove acid insoluble sulfides (e.g. CuS, Bi2S3, CdS, PbS,
HgS, etc.).
To the remaining mix, add (NH4)2S at pH 8 to remove base
insoluble sulfides and hydroxides (e.g. Al(OH)3, Fe(OH)3,
ZnS, NiS, CoS, etc.).
To the remaining mixture add (NH4)2HPO4 to remove
insoluble phosphates (Ba3(PO4)2, Ca3(PO4)2, MgNH4PO4).
The final mixture contains alkali metal ions and NH4+.
Copyright 1999, PRENTICE HALL

Chapter 17

44

Additional Aspects of
Aqueous Equilibria

End of Chapter 17
Copyright 1999, PRENTICE HALL

Chapter 17

45

CAU TRUC
LP VO ELECTRON

Cau truc vo electron


Tnh chat cua cac nguyen to phu thuoc vao s
sap xep va nang lng cua cac electron.
Ta can tm hieu ve cau truc ben trong cua am
may electron

Vay ta a biet g ve nguyen


t?

Hy lap co
Democritus vat chat
cau tao bi cac atomos
Moi loai vat chat co
mot loai atomos rieng
biet

Mo hnh Thompsom
Electron tch ien am di
chuyen trong am may
tch ien dng
Plum-Pudding model

Mo hnhRutherford
Hat nhan co kch thc
nho tch ien dng
Electron di chuyen
xung quanh
Gia electron va hat
nhan la khoang trong

Vay cac electron co trang thai nh the


nao trong nguyen t
Nang lng?
Van toc?
Quy ao di chuyen?

Lam the nao e thay c cau truc ben


trong cua lp vo electron
Nguyen t co kch thc qua nho, ta khong the
nhn thay cau truc ben trong lp vo electron.
Ta da vao cac tnh chat cua nguyen t e xay
dng mo hnh mo phong cau truc lp vo
electron.
Quang pho cua cac nguyen t cho ta d kien ve
cau truc vo electron.

Anh sang
Nghien cu ve anh sang gop phan xay dng mo
hnh vo electron.
Ban chat anh sang la cac bc xa ien t .
Cac bc xa ien t bao gom nhieu loai song, tat
ca eu di chuyen vi van toc 3.00 x 108 m/s ( c)

Song ien t
Bc song ()

Bien o

Tan so
So song di chuyen qua 1 iem trong mot n v
thi gian (giay)
n v (chu ky)/giay hay hertz (hz)
Ky hieu

c =

Lien he gia tan so va bc song


T le nghch
Bc xa co tan so khac nhau se co mau sac
khac nhau (neu nam trong vung kha kien).
Cac bc xa ien t trai ra trong mot dai tan
so rong (goi la QUANG PHO)

QUANG PHO

Nang
lng
cao

NANG
LNG
THAP

Radio Micro Infrared


waves waves .

Tan so thap

Ultra- XGamma
violet Rays Rays

Bc song dai
AS kha kien

tan so cao
Bc song
ngan

V du
CO2 hap thu bc xa co bc song 0.018 mm. Hay
xac nh tan so cua bc xa nay?
8m
3.0010
s = 1.71013 s-1
= c =

0.01810-3 m

n v: 1 Hertz (Hz) 1 s-1


Hay tnh bc song cua song FM co tan so 90.7 MHz.

3.00108 s

= c =
1 = 3.31 m

6
90.710 s

Nang lng bc xa
Theo quan niem co ien, nang lng cua song
phu thuoc vao bien o.
Hieu ng quang ien cho thay nang lng cua
bc xa phu thuoc vao tan so.
Theo Einsteins anh sang la mot chum cac hat
photon, moi hat co nang lng:
Ephoton = h
Hang so Plancks : h = 6.6310-34 Js

V du
Nang lng toi thieu e bt mot electron ra khoi
cesium la 3.0510-19 J. Co the dung anh sang
mau xanh co = 505 nm e bt electron t
cesium hay khong?
6.6310-34 Js 3.00108 m
hc
s
Ephoton = h =
-9
=
50510 m
= 3.9410-19 J

c!

Moi electron b bt ra co ong nang la 0.8910-19


J.

Planck

Einstein

Qua trnh xay dng mo hnh


vo electron da tren cac
nghien cu quang pho

Quang pho anh sang trang

Anh sang trang la to hp cua cac bc xa n sac trong khoang bc song


400 nm (tm) en 700 nm (o). Chieu anh sang trang qua thau knh ta c
quang pho lien tuc cua cac bc xa n sac nay

Pho nguyen t
Cac chat khi b nung
nong phat ra anh sang
co mau sac khac nhau.
Cho chum anh sang
nay qua thau knh se
c mot tap hp cac
vach .

Quang pho vach


ac trng cho moi
nguyen to.

Quang pho vach cua Hydrogen

Mo hnh Bohrs
1913: Bohr a ra mo hnh nham giai thch hien tng
quang pho vach

Bohr

Cac giai thch cua Bohr


Cac electron trong nguyen t chuyen ong tren
cac quy ao co nang lng xac nh.
R
En = 2H
n

Hang so Rydberg :
So th t cua quy ao:

RH = 2.1810-18 J
n = 1,2,3,...

2 Mot electron co the di chuyen t quy ao nay sang


quy ao khac bang cach phat xa hay hap thu cac bc
xa co nang lng ung bang hieu so nang lng gia
hai quy ao.

Cac giai thch cua Bohr

S o
nang lng:

E
0
E4
E3
E2

...

n=
n=4
n=3
n=2

Trang thai
Kch thch

Ephoton = Eelectron
E1

n=1

Trang thai
nen

Quang pho vach Hydrogen


Day Lyman => t ngoai
n > 1 ==> n = 1
Day Balmer => kha kien
n > 2 ==> n = 2
Day Paschen => Hong ngoai
n > 3 ==> n = 3

Cac giai thch cua Bohr

Tan so bc xa tnh theo Bohr

E R H
=
=
h h
Khi ni > nf, phat xa.
Khi nf > ni, hap thu.

1
1

2
2
n
n
f
i

Bai tap ap dung


Tnh bc song dai nhat va ngan nhat khi
eletron di chuyen t mc n=6 en cac mc thap
hn

Bai tap ap dung


Hay xac nh tan so va bc song cua cac bc
xa thuoc day Balmer (kha kien). Biet rang cac
bc xa nay co c do s chuyen electron t
cac mc n=3,4,5,6 ve mc n=2
Cho RH=2.178x10-18 J

Quang pho vach hydrogen

V du
Xac nh bc song cua bc xa phat ra khi electron di
chuyen t quy ao co n = 4 en n = 2?

Ephoton = E = E4 E2 = RH RH
16
4
hc = 3 R

16 H
= 16 hc
3 RH
m
16 6.6310-34 Js 3.00108 s
=
3 2.1810-18 J
Xanh
= 4.8710-7 m = 487 nm

Khiem khuyet cua mo hnh Bohr


Ch ung cho trng hp cua Hydrogen
Khong giai thch c quang pho cua cac
nguyen to khac.
Mot mo hnh mi c xay dng
Mo hnh LNG T
QUANTUM MODEL

Mo hnh LNG T
Da tren ban chat nh nguyen (song hat) cua vat chat

de Broglie

Schrodinger

Heisenberg

Ban chat song cua vat chat


Nam 1925 Louis Debroglie a ra cach nhn mi ve cac
hat vi mo o la va co ban chat hat va co ban chat song.
Theo Debroglie: Neu bc xa co the c coi la cac dong hat
photon th cac hat vi mo nh elctron, proton, neutron cung the
hien tnh chat song
Debroglie cho rang bc song cua hat vi mo la ham so
cua van toc va khoi lng cua no.

h
m V

vi : bc song (m); h: hang so Plank (Js); m: khoi


lng hat (g) ; V van toc hat (m/s)
( 1J = 1 kg m2 /s2)

V du
Tnh bc song chuyen ong cua mot electron
chuyen ong vi van toc 3.00x106 m/s, va mot
qua golf chuyen ong vi van toc 62 m/s.
6.6310-34 Js
e = h = h =
m
p
mv
9.1110-31 kg 3.00108 s
=

2.4210-12

J s 2 = 2.4210-12 m
kg m

6.6310-34 Js
gb =
= 2.410-34 m
m
0.0453 kg 62
s

Nguyen ly bat nh Heisenberg


Ban chat song hat cua hat vi mo a en he qua quan
trong :
Khong the xac nh chnh xac ca v tr va van toc
cua hat
Nguyen ly nay c the hien di dang toan hoc :

h
X V
m

(X: o bat nh ve v tr; V: o bat nh ve van


toc; h: hang so Plank; m: khoi lng cua hat)

Tong Quat
Khi noi ve trang thai chuyen ong cua
electron ta khong the noi ti ng i
chnh xac cua no ma ch co the noi en
xac suat co mat cua no trong
vung khong gian quanh hat nhan.

Phng trnh song Schrdinger


1. c xem la la nh luat c hoc lng t ve s chuyen
ong cua cac hat vi mo.
2. Tng t nh cac nh luat Newton trong c hoc co
ien cho chuyen ong cua cac hat v mo .
3. Trang thai chuyen ong cua electron trong nguyen t
c mo ta bang phng trnh song ng ien t ket
hp vi phng trnh De Broglie.

Phng trnh song Schrdinger


h2 2 2 2
2 ( 2 + 2 + 2 ) + U = E
8 m x
y
z
Vi la ham song ac trng cho trang thai cua electron
E: nang lng toan phan cua electron
U: The nang
h: Hang so Plank
x, y, z: cac thanh phan toa o.
m: khoi lng electron

va gia
Giai phng trnh Schrodinger ta se tm c cac ham so
tr nang lng E tng ng. ac trng cho trang thai chuyen ong
cua electron trong nguyen t

Y ngha cua ham song


Ham song ac trng cho trang thai cua electron trong
nguyen t.
Ta ch co the biet c xac suat co mat cua electron cho
nao trong nguyen t.
ai lng 2
bieu dien mat o xac suat co mat cua
electron trong nguyen t.
Khi 2 cang ln trong vung khong gian nao o th ay
electron se xuat hien thng xuyen hn.

Orbitals : am may electron

Orbitals

n,l,ml2 the hien xac suat tm thay electron tai


vung khong gian quanh hat nhan thng c
goi la orbitals hay am may electron.

12,0,0 (x,y,z)

So lng t
La cac so nguyen co c khi giai phng trnh
song
Co 3 loai so lng t
So lng t chnh: n
So lng t Phu : l
So lng t T ; ml

Mot bo 3 so lng t bieu dien mot orbital

So lng t chnh
Co cac gia tr
n = 1,2,3,....
the hien nang lng cua orbital:
En,l, m = R2H
n
l

Hang so Rydberg : RH = 2.1810-18 J


n cang ln kch thc cua orbital cang ln

So lng t Phu
Co cac gia tr
l = 0,1,2,..., n-1
l xac nh hnh dang cua cac orbital.
Gia tr cua l thng c bieu dien bang cac ch
cai:
l = 0 , 1 , 2 , 3 , 4 ,...
s p d f g

So lng t T
Co cac gia tr
ml = -l, -l+1, ... , l-1, l
ml xac nh s nh hng cua orbital.

Bo cac so lng t va cac orbital tng


ng
n

ml

So
orbital
trong
lp

Ky hieu
lp

Ky hieu van ao

So van
ao
trong
l1p

1s

2s

-1, 0, +1

-1, 0, +1

-2, -1, 0, +1, +2

-1, 0, +1

4px 4py

-2, -1, 0, +1, +2

(4d)

-3, -2, -1, 0, +1,


+2, +3

(4f)

2px 2py
7

2pz

3s
3px 3py

3pz

(3d)
16

4s
4pz

Bieu dien Orbital


Dang o th bieu dien s bien thien cua mat o
electron (Xac suat hien dien cua electron) theo khoang
cach en nhan.

Bieu dien Orbital


Dang khong gian bieu dien vung khong gian tai
o sac xuat tm thay electron la 90%

Orbital S
s orbital co dang hnh cau kch thc tang dan
theo o ln cua n:

1s

2s

3s

Orbital p
orbital p (l = 1) co dang hnh qua ta oi nh
hng theo 3 truc x, y, va z.
Thng ky hieu la px, py, va pz.

Orbital d va f
Co cac hnh dang phc tap.

So lng t Spin
c a ra vao nam 1925
Co 2 gia tr +1/2 va 1/2.

Spin quantum
number:
ms =
Magnetic
Moment

Magnetic
Field
Direction

So lng t Spin

Spin quantum
number:
ms = -
Magnetic
Moment

Magnetic
Field
Direction

Cau truc vo electron theo


quan iem lng t

Vo Electron
Vo electron gom cac lp va phan lp
LP gom cac orbital co cung n
PHAN LP gom cac orbital co cung n va l

Nguyen t 1 electron
n
1

l
0

ml
0

orbital
1s

Nang lng
-RH

2s

-RH/4

-1,0,1

2p

-RH/4

3s

-RH/9

-1,0,1

3p

-RH/9

-2,-1,0,1,2

3d

-RH/9

Nguyen t nhieu Electron


Do co s tng tac gia cac electron, cac phan lp
trong cung mot lp se co nang lng khac nhau:
s<p<d<f

0
E

5s
4s
3s
2s

5p
4p
3p

4d
3d

4f

2p
2p

1s

S sap xep electron trong vo nguyen t


Tuan theo 3 nguyen tac:
Nguyen ly ben vng
Nguyen ly loai tr Pauli
Qui tac Hund

Nguyen ly ben vng


Electron se chiem cac orbital co nang lng
thap trc.
V du:
or

Li:
1s

2s

[He]
2s

Cau hnh electron thng c viet di dang.

Li:

1s2 2s1

or

[He] 2s1

Nguyen ly loai tr Pauli


Trong cung mot nguyen t , khong the co 2
electron co 4 so lng t giong nhau.
Trong mot orbital ch co toi a 2 electron va 2
electron nay phai co spin ngc nhau.
V du: 2 electron trong nguyen t Heli co cac so
lng t
electron 1
electron 2

n l
1 0
1 0

ml ms
0 +
0 -

Qui tac Hund


Cau hnh electron ben la cau hnh co nhieu
electron cha ghep cap nhat.
Carbon:
nang lng cao
1s

2s

2p

Nang lng thap


1s

2s

2p

Cau hnh Electron

Cau hnh electron


Viet cau hnh electron cua:
13Al:

1s2 2s2 2p6 3s2 3p1


[Ne] 3s2 3p1

26Fe:

[Ar] 4s2 3d6

[Ar]
4s

50Sn:
+2
82Pb :
92U:

[Kr] 5s2 4d10 5p2


[Xe] 6s2 4f14 5d10
[Rn] 7s2 6d1 5f3

S o o lng t
Viet cau hnh electron cua Phospho
Lu y Phospho co 15 electron

3d

7s
6s
5s

Nang lng

4s
3s
2s

7p
6p
5p
4p

6d
5d
4d

5f
4f

3d

3p 2 electron au c ien
vao orbital 1s
2p Lu y 2 spin ngc nhau
con 13 electron na

1s

7s
6s
5s

Nang lng

4s
3s
2s
1s

7p
6p
5p
4p

6d
5d
4d

5f
4f

3d

3p 2 electron tiep theo ien


vao orbital 2s
2p con 11 electron na

7s
6s
5s

7p
6p
5p
4p

Nang lng

4s

6d
5d
4d

5f
4f

3d

3p
3s
2p
2s
1s

7s
6s
5s

7p
6p

6d

5p

4d

4p

Nang lng

4s
3p
3s
2p
2s
1s

5d

3d

5f
4f

7p
6p

7s
6s
5s

6d
5d

5p

4d

4p

3d

Nang lng

4s
3p

Cau hnh electron


2p 1s22s22p63s23p3

3s
2s
1s

Qui tac Kleskovski


7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

1s2

2 electrons

5f
4f

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

1s2 2s2

4 electrons

1s2 2s2 2p6 3s2

12 electrons

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

1s2 2s2 2p6 3s2


3p6 4s2

20 electrons

1s2 2s2 2p6 3s2


3p6 4s2 3d10 4p6
5s2
38 electrons

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

1s2 2s2 2p6 3s2


3p6 4s2 3d10 4p6
5s2 4d10 5p6 6s2
56 electrons

1s2 2s2 2p6 3s2


3p6 4s2 3d10 4p6
5s2 4d10 5p6 6s2
4f14 5d10 6p6 7s2
88 electrons

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s

1s2 2s2 2p6 3s2


3p6 4s2 3d10 4p6
5s2 4d10 5p6 6s2
4f14 5d10 6p6 7s2
5f14 6d10 7p6
108 electrons

V du
Viet cau hnh electron cua:

Fe
Fe2+
ClS2Ti

S PHAT TRIEN CUA CAC


LY THUYET TRONG
KHOA HOC THC NGHIEM

CAC BC PHAT TRIEN


Bc 1: Quan sat ( nh tnh + nh lng)
Bc 2: Neu gia thuyet neu cac giai thch
hp ly cho cac hien tng quan sat c
Bc 3: Thc nghiem: kiem tra lai tnh chnh
xac cua cac gia thuyet
e hieu c mot hien tng, 3 bc tren
c lap lai nhieu lan. T cac kien thc tch
luy c se a ra cach giai thch hp ly cho
hien tng.

NH LUAT T NHIEN
Mot so hien tng xay ra theo nhng
trat t xac nh va co nhng tnh chat
nhat nh khong thay oi c tong hp
lai thanh nhng NH LUAT T
NHIEN

LY THUYET
Nhng giai thch hp ly cho cac hien tng
xay ra trong t nhien.
Thay oi t t cung vi cac thong tin thu
nhan c khi quan sat cac hien tng t
nhien.
Cac thc nghiem c tien hanh lien tuc e
lam hoan thien them cho LY THUYET vi hy
vong se tien gan en viec hieu ro ban chat
cua cac hien tng t nhien.

QUAN SAT
GIA THUYET

NH LUAT
T NHIEN

THC NGHIEM

LY THUYET (mo
hnh)

HIEU CHNH LY
THUYET

TIEN OAN

THC
NGHIEM

THUYET OXY VE S CHAY


Stahl : (1703) Thuyt Phlogiston
Cavendish, Black: (1755) CO2
Priestley: (1774) : O2
Lavoisier : (1785) Thuyt Oxy

THUYET PHLOGISTON
Georg Ernst Stahl (1660-1734)
Cac chat chay c la nh co cha chat chay
(Phlogiston). Khi vat the chay, phlogiston bay ra,
chuyen ong xoay va ket hp vi khong kh tao
thanh cai ma ta thng goi la ngon la.
Phlogiston khong giong nh mot vat chat cu the
nao, no ch co tnh chat vat chat khi no ket hp
vi mot chat khac trong vat the hon hp, luc o
no the hien di dang ngon la khi nung nong.
trang thai t do th phlogiston la mot th khong
xac nh, khong cu the.

THUYET PHLOGISTON (cont.)


Tat ca cac chat chay c hoac khi nung nong b bien oi
eu co thanh phan gom 2 chat la x va Phlogiston. Than
hau nh hoan toan gom Phlogiston va cha rat t x, con
cac kim loai ngc lai cha chu yeu la x va rat t
Phlogiston.
Khi ot chay than, phlogiston trong than chuyen vao
khong kh, con lai mot t x la tro:
Than  Phlogiston + X (tro)
Khi nung kim loai qua trnh cung xay ra tng t
Sat  Phlogiston + X (sat oxit)
Khi nung x cua mot kim loai vi than se thu c kim loai
la do phlogiston se c chuyen vao x lam phuc hoi kim
loai
X (sat oxit) + Phlogiston (than)  Kim loai (sat)

MAU THUAN TRONG THUYET


PHLOGISTON
MOT SO CHAT SAU KHI CHAY LAI
TNG KHOI LNG
STAHL GIAI THCH:
Trong mot so trng hp Phlogiston co
khoi lng am

Cac bc phat trien cua thuyet Oxy


Black (1755): Khong kh co the co
nh (CO2)
Cavendish (1766) : Khong kh chay
(Hidro)
Priestley (1774 ): khong kh song
(Oxy)

Lavoisier: (1777)
Bat c s chay nao cung giai phong ra
chat la va anh sang
Qua trnh chay ch xay ra trong mot dang
khong kh ma Priestley goi la khong kh
a mat Phlogiston (dephlogisticated air)
va Lavoisier goi la khong kh tinh
khiet (pure air). Vat the khong the chay
trong chan khong hay mot th khong kh
khac.

Lavoisier
Trong bat c qua trnh chay nao cung
xay ra s pha huy khong kh tinh khiet
va trong lng vat the tang len ve gia
tr ung bang trong lng cua khong kh
a b hap thu.

Lavoisier
Trong bat ky qua trnh chay nao vat the chay
cung bien thanh axit. V du san pham cua s ot
lu huynh la la axit sunfuaric, phospho chay cho
ra axit phosphoric. S nung nong kim loai cung
tuan theo cac nh luat nay va co the coi o la qua
trnh chay cham. Tuy nhien trong trng hp
nung kim loai th khong kh tinh khiet tac dung
vi kim loai khong tao thanh axit ma tao thanh x
kim loai (metallic Calx).

THUYET CHAY HIEN NAY

Cac chat chay la do ket hp vi


Oxy

Cac loai vat chat

S PHAT TRIEN CUA KHAI NIEM


NGUYEN T
Trung quoc: Ngu hanh (Kim-Moc-ThuyHoa-Tho)
Hy Lap:
Aristos: La-Khong Kh- at- Nc
Democris: Atomos

Dalton

THUYET NGUYEN T DALTON (1808)


Moi nguyen to c cau tao bi nhng hat nho
goi la nguyen t
Cac nguyen t cua cung mot nguyen to th
giong nhau. Cac nguyen t cua cac nguyen to
khac nhau th khac nhau
Cac hp chat hoa hoc c hnh thanh khi cac
nguyen t lien ket vi nhau. Mot hp chat luon
cha mot ty le xac nh cac loai nguyen t
Phan ng hoa hoc xay ra do s thay oi lien
ket gia cac nguyen t. Ban than nguyen t
khong b bien oi trong cac phan ng hoa hoc.

C S CUA VIEC PHAT HIEN RA


ELECTRON
1895: Roentgen phat hien ra tia X
1896: Becquerel phat hien ra hien tng
phong xa

1897: Thomson vi th nghiem tia am cc


phat hien ra electron mang ien tch am

ONG PHONG TIA AM CC CUA


THOMSON

Th Nghiem Thomson
ien ap cao

+
Ong chan khong
a kim loai

Th Nghiem Thomson
ien ap cao

Th Nghiem Thomson
ien ap cao

Th Nghiem Thomson
ien ap cao

Th Nghiem Thomson
ien ap cao

Th Nghiem Thomson
ien ap cao

Th Nghiem Thomson

ien ap
cao

Th Nghiem Thomson
ien ap cao

at vao ien trng

Th Nghiem Thomson
ien ap cao

at vao ien trng

Th Nghiem Thomson
ien ap cao

at vao ien trng

Th Nghiem Thomson
ien ap cao

at vao ien trng

Th Nghiem Thomson
ien ap cao

at vao ien trng

Th Nghiem Thomson
ien ap cao
+

at vao ien trng

Th Nghiem Thomson
ien ap cao

at vao ien trng


Dong hat mang ien am

Mo hnh Thomson
Phat hien electron (mang
ien am)
Khong phat hien ra cac hat
mang ien dng
Thomson cho rang cac
electron di chuyen trong mot
am may tch ien dng
Tng t nh hnh anh mot
cai banh Pudding

S TACH CAC TIA PHONG XA

1911: Rutherford dung tia ban qua


la vang dat mong  s co mat cua hat
nhan mang ien dng

Buong
ch

Man huynh quang

Uranium
La vang

D oan
Cac hat alpha se de dang xuyen qua la
vang
Ly do
ien tch dng c trai rong trong am
may

D oan

Ly do

Ket qua thc nghiem

Giai thch ket qua thc nghiem


Phan ln the tch
trong nguyen t la
khoang trong
Hat nhan co kch
thc nho (cau truc
chac ac) nam gia
Cac hat alpha se b
lech hng khi tiep
can gan hat nhan

Mo hnh cau tao nguyen t

am may
electron

1919: Rutherford phat hien ra


hat proton mang ien dng

1932: Chadwich khi ban pha


mieng kim loai Berili bang tia a
phat hien ra hat neutron trung hoa
ien.

CAC HAT C BAN TRONG


NGUYEN T
Hat

Khoi lng
(kg)

ien tch

Khoi lng
(amu)

Electron

9.1095x10-31

- 1.602x10-19 C

5.486x10-4

Proton

1.6726x10-27

+ 1.602x10-19 C

1.0073

neutron

1.6750x10-27

1.0087

Amu (atomic mass unit) = 1.66054x10-24 gam

Kch thc nguyen t


ng knh nguyen t khoang 1 x 10-10 en
5 x 10-10 m (1 en 5 angstron).

V du so sanh kch thc nguyen t


Mot cai au but bi co ng knh 1 x 10-3 m (1
mm). Neu 1 nguyen t co ng knh 2.5 x 10-10
m, th
(1 nt/2.5 x 10-10 m) * (1 x 10-3 m) = 4 x 106 nt
Tc la co 4 trieu nguyen t sap xep doc theo
ng knh cua au bi.

o chac ac cua hat nhan


ng knh hat nhan khoang 10-4 . Nh vay,
ng knh hat nhan bang 0.01% ng knh
cua toan nguyen t. Neu hat nhan co ng
knh bang au but bi th ng knh cua nguyen
t tng ng se la 10 m
Nh vay hat nhan se co o chac ac rat cao
Hay xet khoi lng rieng cua 1 hat nhan n
gian gom 1 proton va 1 neutron:

Khoi lng rieng cua hat nhan


Khoi lng hat nhan = ~2.0 amu = 2 * (1.66 x 10-24 g) = 3.32 x
10-24 g
ng knh hat nhan = (khoang) 1 x 10-4 A = 1 x 10-14 m
Ban knh hat nhan = 1 x 10-14 m/2 = 0.5 x 10-14 m
The tch hat nhan = (4/3) x 3.14 x (ban knh hat nhan)3
The tch hat nhan = 5.24 x 10-43 m3
Khoi lng/the tch = 3.32 x 10-24 g/5.24 x 10-43 m3
Khoi lng/the tch = 6.34 x 1018 g/m3
Mot vien xuc xac co the tch 1 cm3, hay 1 x 10-6 m3 neu c
cau tao hoan toan bang hat nhan se co khoi lng
(6.34 x 1018 g/m3) * (1 x 10-6 m3) = 6.34 x 1012 g
= 6.34 trieu tan

KY HIEU NGUYEN T

A
z

X: ky hieu ten nguyen to


Z: n v ien tch hat nhan = so proton = so
electron cua nguyen t
A: So khoi = so proton + so neutron

ONG V
Cac nguyen t co cung so proton nhng
khac so neutron

Xac nh khoi lng va phan tram


cac ong v
may khoi pho

V du :Clo co 2 ong v Cl-35 va Cl-37,


co khoi lng lan lt la 34.96885
va36.96590 amu. Khoi lng nguyen t
trung bnh cuaClo la 35.453 amu. Hay
tnh phan tram moi ong v trong t
nhien

Goi x = % Cl-35
y = % Cl-37
x + y = 1 <=> y = 1 - x
(M Cl-35)(% Cl-35) + (M Cl-37)(% Cl-37) = 35.453
34.96885*x + 36.96590*y = 35.453
34.96885*x + 36.96590*(1-x) = 35.453
(34.96885 - 36.96590)x + 36.96590 = 35.453
(34.96885 - 36.96590)x = (35.453 - 36.96590)
- 1.99705x = - 1.5129
1.99705x = 1.5129
x = 0.7553 <=> 75.53% Cl-35
y = 1 - x = 1.0000 - 0.7553 = 0.2447
24.47% Cl-37

Bai tap 1
Tnh khoi lng nguyen t trung bnh cua cac nguyen to
sau ay:
a) Iridi: 191Ir (37,3%), 193Ir (62,7%).
b) Antimon: 121Sb (57,25%), 123Sb (42,75%).
c) Bac: 107Ag (51,82%), 109Ag (48,18%).
d) Argon: 36Ar (0,34%), 38Ar (0,07%), 40Ar (99,59%).
e) Sat: 54Fe (5,85%), 56Fe (91,68%), 57Fe (2,17%),
58Fe (0,41%).
f) Niken: 58Ni (67.76%), 60Ni (26,16%), 61Ni (2,42%),
62Ni (3,66%).

Bai tap 2
ong co hai ong v 63Cu va 65Cu,
khoi lng nguyen t trung bnh
cua ong la 63,54. Tm thanh
phan phan tram cua moi loai
ong v.

S:
63Cu

= 73%;

65Cu

= 27%

Bai tap 3
Nguyen to Mg co 3 loai ong v, so khoi lan
lt la 24, 25, 26. Trong so 5000 nguyen
t Mg th co 3930 ong v 24 va 505 ong
v 25, con lai la ong v 26. Tnh khoi
lng nguyen t trung bnh cua Mg.

S:

Mg = 24,183

Bai tuan ti

Cau truc lp vo
electron

Cau hoi chuan b


Da vao nhng ly luan va thc nghiem
nao e xac nh c trang thai cua cac
electron trong nguyen t.
Orbital (van ao) la g. Lam the nao e
xac nh c hnh dang cua cac orbital
(vd: orbital S hnh cau, orbital P hnh qua
ta oi)

CN BNG HO HC

HO I CNG A2

CHNG II

Khi nim v cn bng


Quan st kh khng mu c lm ng lnh
N2O4. Ti nhit phng, kh ny b phn hy
thnh kh NO2 mu nu:
N2O4(g) 2NO2(g).
Ti mt lc no , mu sc ngng thay i, v
chng ta c mt hn hp N2O4 and NO2. Ta ni
phn ng t cn bng.
Cn bng ho hc l im m ti nng cc
cht khng thay i na.

HO I CNG A2

CHNG II

Trn quan im ca thuyt va chm:


Khi lng NO2 tng ln, c kh nng 2
phn t NO2 va p vo nhau to thnh
N2O4.
Ti thi im ban u cha c N2O4 nn
phn ng nghch 2NO2(g) N2O4(g) cha
xy ra.

HO I CNG A2

CHNG II

The Concept of Equilibrium

HO I CNG A2

CHNG II

Ti im m tc phn ng phn hy:


N2O4(g) 2NO2(g)
bng vi tc phn ng nghch:
2NO2(g) N2O4(g).
tn ti mt cn bng ng (dynamic equilibrium)
cn bng l ng v phn ng khng h b ngng
li. Lc mi tc thun nghch l nh nhau
Ti cn bng, bao nhiu N2O4 phn ng to
thnh NO2 th c by nhiu NO2 phn ng to
li N2O4:

N2O4(g)
HO I CNG A2

2NO2(g)
CHNG II

Khi nim v cn bng

HO I CNG A2

CHNG II

Tom lai:
 Can bang co tnh chat ong, ngha la luc can bang ve
mat thc te thanh phan cac hp chat khong thay oi
nhng thc te phan ng van xay ra vi vthuan va
vnghch bang nhau.
 Khuynh hng t nhien cua mot phan ng hoa hoc
la luon hng ti can bang.
 Can bang se at c khi G=0. Luc nay can bang
hoa hoc la s can bang gia hai yeu to anh hng len
phan ng la nhiet va entropy.

HO I CNG A2

CHNG II

Hng s cn bng

Xem phn ng

N2(g) + 3H2(g)

2NH3(g)

a) Nu ta bt u bng mt hn hp nitrogen v
hydrogen (t l bt k), phn ng s t ti
cn bng tng ng vi nng khng i
ca nitrogen, hydrogen v ammonia.
b) Tuy nhin nu ban u ta ch c ammonia v
khng nitrogen hay hydrogen, phn ng vn
xy ra. N2 v H2 c to thnh cho ti khi cc
nng t ti cn bng

HO I CNG A2

CHNG II

Hng s cn bng

HO I CNG A2

CHNG II

Hng s cn bng
D thnh phn tc cht ban u v thnh phn
sn phm ra sao, cc nng lun t ti mt t
l nh nhau ti cn bng
Cho mt phn ng bt k

aA + bB(g)

pP + qQ

Biu thc ca hng s cn bng l

P ] p [Q]q
[
Kc =
[A]a [B]b
vi Kc l hng s cn bng
HO I CNG A2

CHNG II

10

ln ca hng s cn bng
Hng s cn bng, K, l t l ca sn phm
trn tc cht. Do :
K cng ln th ti cn bng nng sn
phm cng ln.
Ngc li, K cng nh th ti cn bng nng
tc cht cng ln
Nu K >> 1, cc sn phm chim u th ti
cn bng v cn bng chuyn sang phi
Nu K << 1, cc tc cht chim u th ti
cn bng v cn bng chuyn sang tri
HO I CNG A2

CHNG II

11

The Equilibrium Constant

HO I CNG A2

CHNG II

12

Can bang ong the trong dung dch:

Xet phan ng:


mA + nB pC + qD
co :vt = kt [A]m[B]n
vn = kn [C]p[D]q
[C]p[D]q
tai can bang : vt = vn  Kc = kt / kn = ------------[A]m[B]n
[C]p[D]q
Vay:
Kc = ------------[A]m[B]n
trong o Kc=hang so can bang theo nong o.

HO I CNG A2

CHNG II

13

Can bang ong the trong pha kh:


Lien he en ap suat rieng phan cua hp chat.

KP

( PP ) p (PQ )q
=
( PA )a ( PB )b
PA = [A](RT)

HO I CNG A2

CHNG II

14

Can bang d the:


Trong trng hp can bang co s hien dien cua chat
kh, trong bieu thc Kc ngi ta ch chu y ti chat
kh ma thoi.

CaCO3(s)

Kc =

[CaO]
[CaCO3 ]

CaO(s) + CO2(g)

[CO 2 ] = constant [CO 2 ].

K c = K c constant = [CO 2 ]
HO I CNG A2

CHNG II

15

The Equilibrium Constant


Heterogeneous Equilibria

HO I CNG A2

CHNG II

16

Hang so can bang va nang lng t do G


Ta co:
Gr = Gor + RT lnKcb
Tai can bang: 0 = Gor + RT lnKcb
hay
Gor= RT lnKcb

Kcb = Kc hay Kp

Kcb = e-Go/ RT

HO I CNG A2

CHNG II

17

ng dung cua hang so can bang trong hoa hoc


D oan chieu phan ng
We define Q, the reaction quotient, for a general reaction

aA + bB(g)

pP + qQ

as

[
P ] p [Q]q
Q=
[A]a [B]b
where [A], [B], [P], and [Q] are molarities at any time.
Q = K only at equilibrium.
HO I CNG A2

CHNG II

18

Applications of Equilibrium Constants


Predicting the Direction of Reaction
If Q > K then the reverse reaction must occur to reach
equilibrium (i.e., products are consumed, reactants
are formed, the numerator in the equilibrium
constant expression decreases and Q decreases until it
equals K).
If Q < K then the forward reaction must occur to
reach equilibrium.

HO I CNG A2

CHNG II

19

Xac nh nong o cac chat mc can bang:


Co Go, R, T => Kc, Kp => [ ] cac chat.

HO I CNG A2

CHNG II

20

Le Chteliers Principle
Xem

N2(g) + 3H2(g)

2NH3(g)

As the pressure increases, the amount of ammonia


present at equilibrium increases.
As the temperature decreases, the amount of
ammonia at equilibrium increases.
Can this be predicted?
Nguyen ly Le Chatelier: Trong mot phan ng can
bang, neu thay oi mot yeu to lam xao tron mc can
bang se lam can bang di oi theo chieu chong lai s
thay oi ay.
HO I CNG A2

CHNG II

21

Le Chteliers Principle

HO I CNG A2

CHNG II

22

Le Chteliers Principle
Change in Reactant or Product Concentrations
Consider the Haber process

N2(g) + 3H2(g)

2NH3(g)

If H2 is added while the system is at equilibrium, the


system must respond to counteract the added H2 (by
Le Chtelier).
That is, the system must consume the H2 and produce
products until a new equilibrium is established.
Therefore, [H2] and [N2] will decrease and [NH3]
increases.

HO I CNG A2

CHNG II

23

Le Chteliers Principle
Change in Reactant or Product Concentrations

HO I CNG A2

CHNG II

24

Le Chteliers Principle
Change in Reactant or Product Concentrations
Adding a reactant or product shifts the equilibrium
away from the increase.
Removing a reactant or product shifts the equilibrium
towards the decrease.
To optimize the amount of product at equilibrium, we
need to flood the reaction vessel with reactant and
continuously remove product (Le Chtelier).
We illustrate the concept with the industrial
preparation of ammonia

N2(g) + 3H2(g)
HO I CNG A2

CHNG II

2NH3(g)
25

Le Chteliers Principle
Change in Reactant or Product Concentrations

HO I CNG A2

CHNG II

26

Le Chteliers Principle
Change in Reactant or Product Concentrations
N2 and H2 are pumped into a chamber.
The pre-heated gases are passed through a heating
coil to the catalyst bed.
The catalyst bed is kept at 460 - 550 C under high
pressure.
The product gas stream (containing N2, H2 and NH3)
is passed over a cooler to a refrigeration unit.
In the refrigeration unit, ammonia liquefies but not
N2 or H2.
HO I CNG A2

CHNG II

27

Le Chteliers Principle
Change in Reactant or Product Concentrations
The unreacted nitrogen and hydrogen are recycled
with the new N2 and H2 feed gas.
The equilibrium amount of ammonia is optimized
because the product (NH3) is continually removed and
the reactants (N2 and H2) are continually being added.

Effects of Volume and Pressure


As volume is decreased pressure increases.
Le Chteliers Principle: if pressure is increased the
system will shift to counteract the increase.
HO I CNG A2

CHNG II

28

Le Chteliers Principle
Effects of Volume and Pressure
That is, the system shifts to remove gases and
decrease pressure.
An increase in pressure favors the direction that has
fewer moles of gas.
In a reaction with the same number of product and
reactant moles of gas, pressure has no effect.
Consider

N2O4(g)

HO I CNG A2

2NO2(g)

CHNG II

29

Le Chteliers Principle
Effects of Volume and Pressure
An increase in pressure (by decreasing the volume)
favors the formation of colorless N2O4.
The instant the pressure increases, the system is not at
equilibrium and the concentration of both gases has
increased.
The system moves to reduce the number moles of gas
(i.e. the forward reaction is favored).
A new equilibrium is established in which the mixture
is lighter because colorless N2O4 is favored.

HO I CNG A2

CHNG II

30

Le Chteliers Principle
Effect of Temperature Changes
The equilibrium constant is temperature dependent.
For an endothermic reaction, H > 0 and heat can be
considered as a reactant.
For an exothermic reaction, H < 0 and heat can be
considered as a product.
Adding heat (i.e. heating the vessel) favors away from
the increase:
if H > 0, adding heat favors the forward reaction,
if H < 0, adding heat favors the reverse reaction.

HO I CNG A2

CHNG II

31

Le Chteliers Principle
Effect of Temperature Changes
Removing heat (i.e. cooling the vessel), favors towards
the decrease:
if H > 0, cooling favors the reverse reaction,
if H < 0, cooling favors the forward reaction.

Consider

CoCl42-(aq) + 6H2O(l)

Cr(H2O)6(aq) + 4Cl-(aq)
for which H > 0.

Co(H2O)62+ is pale pink and CoCl42- is blue.

HO I CNG A2

CHNG II

32

Le Chteliers Principle
Effect of Temperature Changes

HO I CNG A2

CHNG II

33

Le Chteliers Principle
Effect of Temperature Changes
Cr(H2O)6(aq) + 4Cl-(aq)
CoCl42-(aq) + 6H2O(l)
If a light purple room temperature equilibrium mixture is
placed in a beaker of warm water, the mixture turns deep
blue.
Since H > 0 (endothermic), adding heat favors the forward
reaction, i.e. the formation of blue CoCl42-.
If the room temperature equilibrium mixture is placed in a
beaker of ice water, the mixture turns bright pink.
Since H > 0, removing heat favors the reverse reaction
which is the formation of pink Co(H2O)62+.

HO I CNG A2

CHNG II

34

Le Chteliers Principle
The Effect of Catalysts
A catalyst lowers the activation energy barrier for the
reaction.
Therefore, a catalyst will decrease the time taken to
reach equilibrium.
A catalyst does not effect the composition of the
equilibrium mixture.

HO I CNG A2

CHNG II

35

TRNG THI KH

Ho i Cng A1

H Th Cm Hoi, PhD

Cc tnh cht ca kh
Mi vt cht tn ti 3 pha: rn, lng v
kh.
Cc cht kh d b nn, p v phn b
trong ton b th tch vt cha chng.
Khi mt cht kh b nn, th tch ca n
gim.
Cc cht kh lun lun to hn hp ng
th vi cc cht kh khc.
H Th Cm Hoi, PhD

H Th Cm Hoi, PhD

H Th Cm Hoi, PhD

P SUT
p sut khng kh v kh p k (barometer)
p sut l lc tc dng trn mt n v din
tch:

P=

F
A

Trng lc to nn mt lc ln kh quyn ca tri


t.
Mt ct khng kh tit din 1 m2 to nn mt lc
l 105 N.
p sut ca ct khng kh 1 m2 l 100 kPa.
H Th Cm Hoi, PhD

p sut
p sut khng kh v kh p k (barometer)

H Th Cm Hoi, PhD

p sut
p sut khng kh v kh p k (barometer)
H n v SI : 1 N = 1 kg.m/s2; 1 Pa = 1 N/m2.
p sut khng kh c o bi p k
(barometer)
Nu mt ct (mao qun) nhng trong mt vt
cha thy ngn thng vi kh quyn, mc thy
ngn s dng ln n 760 mm trong ct.
p sut chun ca kh quyn l p sut to
c mc thu ngn l 760 mm of Hg trong ct.

H Th Cm Hoi, PhD

n v:
SI: 1 pascal (Pa) = 1 N/m2
Thng thng :1 atm = 760 mm Hg
= 760 torr
= 14.7 lb/in2 (psi)
= 101.325 kPa
= 1.013 bar

H Th Cm Hoi, PhD

p sut
p sut khng kh v kh p k (barometer)

H Th Cm Hoi, PhD

p sut
p sut ca cc kh trong h kn v p k
(Manometer)
p sut ca cc kh trong h khng thng vi kh
quyn c o bng p k (manometers).
Mt p k gm mt bu cha kh gn vo mt ng
hnh ch U (U-tube) cha Hg.
Nu ng hnh ch U ng, p sut ca kh l s
chnh lch ca chiu cao cht lng trong ct
(thng l thy ngn)
Nu ng hnh ch U m thng vi kh quyn, ta s
dng h thc sau:
Nu Pgas < Patm th Pgas + Ph2 = Patm.
Nu Pgas > Patm th Pgas = Patm + Ph2.
H Th Cm Hoi, PhD

10

p sut
p sut ca cc kh trong h kn v p k
(Manometer)

H Th Cm Hoi, PhD

11

Cc nh lut ca cht kh
Mi lin h gia th tch v p sut: nh
lut Boyle (Robert Boyle, 1662)
nh lut Boyle: Th tch ca mt lng cht kh
nht nh th t l nghch vi p sut ca n (ti
nhit khng i) .

H Th Cm Hoi, PhD

12

Cc nh lut ca cht kh
Mi lin h gia th tch v p sut: nh lut
Boyle
Biu thc ton hc:

V = constant

1
P

PV = constant

P1V1 = P2V2 (at constant T)


th ca V theo P l mt hyperbola.
Tng t, th ca V theo 1/P phi l mt
ng thng i qua gc to
H Th Cm Hoi, PhD

13

The Gas Laws


The PressuresPressures-Volume Relationship: Boyles Law

H Th Cm Hoi, PhD

14

Cc nh lut ca cht kh
Mi lin h gia th tch v nhit : nh lut
Charles (Jacques Charles, 1787)
Chng ta u bit rng kh trong khinh kh cu
n ra khi c t nng.
nh lut Charles : Th tch ca mt lng cht
kh nht nh ti p sut khng i tng khi
nhit tng
Biu thc ton hc:

V
= constant
T

V = constant T
(at constant P)

H Th Cm Hoi, PhD

15

Cc nh lut ca cht kh
The TemperatureTemperature-Volume Relationship:
Charless Law
th ca V theo T l mt ng thng
Khi T c o bng C, th ct trc honh ti
nhit l -273.15C.
Chng ta nh ngha khng tuyt i
(absolute zero), 0 K = -273.15C.

H Th Cm Hoi, PhD

16

The Gas Laws

H Th Cm Hoi, PhD

17

Cc nh lut ca cht kh
Mi lin h gia s lng v th tch:
tch: nh lut
Avogadro
nh lut Gay-Lussac v kt hp th tch: Ti
nhit v p sut xc nh, th tch ca cc
kh tham gia phn ng tng ng vi h s t
lng.

H Th Cm Hoi, PhD

18

Gi thuyt ca Avogadro: nhng th tch nh


nhau ca cc cht kh ti cng nhit v p
sut th cha cng s lng phn t cht kh.
nh lut Avogadro: Th tch ca cht kh ti
nhit v p sut xc nh th t l vi s mol
ca cht kh

V = constant n.
22.4 L cht kh bt k ti 25C lun cha 6.02 1023
phn t kh.

H Th Cm Hoi, PhD

19

Phng trnh kh l tng


Cc nh lut:
Boyle: V 1/P
Charles: V T
Avogadro: V n
Kt hp li:

(constant n, T)
(constant n, P)
(constant P, T).

nT
V
P

Phng trnh kh l tng:

nT
V = R

P
H Th Cm Hoi, PhD

20

Phng trnh kh l tng

PV = nRT.
R = hng s kh l tng = 0.08206 L*atm/mol*K.
R
= 82.06 mL*atm/mol*K
= 8.314 J/mol*K
= 1.987 cal/mol*K
STP (standard temperature and pressure)
= 0C, 273.15 K, 1 atm.
Th tch ca 1 mol kh ti STP is 22.4 L.

H Th Cm Hoi, PhD

21

ng dng ca nh lut kh l tng


T trng ca kh v khi lng phn t:
T trng c n v l khi lng trn th tch
Nhn 2 v ca phng trnh kh l tng vi M
(khi lng phn t), chng ta c:

n
P
=
V RT
nM
PM
=d =
V
RT
H Th Cm Hoi, PhD

22

Khi lng phn t ca mt cht kh nh vy


c th xc inh nh sau:

M =

dRT
P

H Th Cm Hoi, PhD

23

Hn hp kh v p sut ring phn


(Gas Mixtures and Partial Pressures)
V cc phn t kh phn b xa nhau nn chng ta
c th xem nh chng c lp vi nhau.
nh lut Dalton: p sut tng cng ca mt hn
hp kh th bng tng p sut ring phn ca mi
kh trong thnh phn hn hp .
Pt = P1 + P2 + P3 +
RT
Mi kh u tun theo PT kh l tng: Pi = ni

V
Combining equations:

RT
Pt = (n1 + n2 + n3 + L)

H Th Cm Hoi, PhD

24

H Th Cm Hoi, PhD

25

p sut ring phn v phn mol (Mole Fractions)


Gi ni l s mol ca kh i to nn p sut ring phn
Pi, th
Pi = iPt,
vi: i l phn mol(ni/nt).

Collecting Gases over Water


Sau khi c tin hnh tng hp, cc kh thng
c sc qua nc.
tnh ton chnh xc lng kh to thnh, chng ta
cn hiu chnh thnh phn p sut ring phn ca
nc.
Ptotal = Pgas + Pwater
H Th Cm Hoi, PhD

26

Gas Mixtures and Partial Pressures


Collecting Gases over Water

H Th Cm Hoi, PhD

27

Thuyt ng hc phn t
Kinetic--Molecular Theory
Kinetic
L l thuyt c xy dng nhm gii thch tnh
cht cc cht kh
L l thuyt ca cc phn t chuyn ng.
Cc gi nh:
Cc kh gm lng rt ln cc phn t chuyn ng
khng ngng.
Th tch ca cc phn t rt nh so vi th tch vt
cha.
Cc lc lin phn t c th b qua.
Nng lng c th c chuyn i gia cc phn
t nhng tng ng nng la khng i ti nhit
xc nh.
ng nng trung bnh ca cc phn t t l thun vi
H Th Cm Hoi, PhD
28
nhit .

Kinetic--Molecular Theory
Kinetic
Kinetic molecular theory
gives us an understanding of
pressure and temperature
on the molecular level.
Pressure of a gas results
from the number of
collisions per unit time on
the walls of container.

H Th Cm Hoi, PhD

29

Thuyt ng hc phn t
mnh ca p sut ph thuc vo s lng
v mnh ca cc va chm ca cc phn t.
Cc phn t kh s hu chung gi tr ng nng
trung bnh.
Mi phn t kh c nng lng khc nhau.
Khi nhit tng, ng nng trung bnh ca cc
phn t kh tng ln.

H Th Cm Hoi, PhD

30

Kinetic--Molecular Theory
Kinetic

H Th Cm Hoi, PhD

31

Thuyt ng hc phn t
Khi ng nng tng, vn tc ca cc phn t kh
tng
Vn tc trung bnh, u, l vn tc ca mt phn
t kh c ng nng trung bnh lin h qua h
thc
= mu2

H Th Cm Hoi, PhD

32

Kinetic--Molecular Theory
Kinetic
Application to the Gas Laws
As volume increases at constant temperature, the
average kinetic of the gas remains constant.
Therefore, u is constant. However, volume increases
so the gas molecules have to travel further to hit the
walls of the container. Therefore, pressure decreases.
If temperature increases at constant volume, the
average kinetic energy of the gas molecules increases.
Therefore, there are more collisions with the container
walls and the pressure increases.

H Th Cm Hoi, PhD

33

Khi ng nng tng, vn tc ca cc phn t kh


tng.
ng nng trung bnh ca mt cht kh c lin
h vi khi lng ca n:
= mu2.
Xt hai kh ti cng nhit , kh nh hn c vn
tc ln hn.

3 RT
u=
M
H Th Cm Hoi, PhD

34

Molecular Effusion and Diffusion

H Th Cm Hoi, PhD

35

Kh thc: S sai bit vi kh l tng


Phng trnh kh l tng:

PV
=n
RT
Cho 1 mol of kh, PV/RT = 1 ti mi p sut.
i vi kh thc, PV/RT thay i ty loi kh. p
sut cng cao, s sai bit cng nhiu.
Do: kh thc c mt gi tr th tch ti hn ti T=0 v
s tn ti lc ht lin phn t gia cc phn t kh
H Th Cm Hoi, PhD

36

Real Gases: Deviations from Ideal


Behavior

H Th Cm Hoi, PhD

37

Phng trnh kh l tng

PV
=n
RT
Cho 1 mol of kh, PV/RT = 1 ti mi nhit .
i vi kh thc, khi T tng cc kh tr nn
ging kh l tng hn.

H Th Cm Hoi, PhD

38

Real Gases: Deviations from Ideal


Behavior

H Th Cm Hoi, PhD

39

Real Gases: Deviations from Ideal


Behavior
Khi tng p sut, cc phn t kh b p li gn
nhau hn.
Khi cc phn t gn nhau hn, th tch ca vt
cha nh li.
Vt cha nh hn, phn t kh chim ch nhiu
hn trc, cc phn t kh gn nhau hn,
khong cch lin phn t gim xung, lc hp
dn xut hin gia cc phn t, kh t ging kh
l tng hn.
H Th Cm Hoi, PhD

40

Real Gases: Deviations from Ideal


Behavior

H Th Cm Hoi, PhD

41

Real Gases: Deviations from Ideal


Behavior
Khi tng nhit , cc phn t kh chuyn
ng nhanh v xa nhau hn.
Nhit tng cng tng nng lng b
gy lc lin phn t.
Do , nhit tng kh cng ging kh l
tng.

H Th Cm Hoi, PhD

42

Real Gases: Deviations from Ideal


Behavior

H Th Cm Hoi, PhD

43

Phng trnh van der Waals


Hai yu t thm vo phng trnh kh l tng
hiu chnh th tch cc phn t v lc hp
dn lin phn t

nRT n 2a
P=

V nb V 2
vi a and b l nhng hng s thc nghim

H Th Cm Hoi, PhD

44

hiu nh hng ca lc lin phn t ln p


sut, ta thy khi mt phn t va chm vo
thnh bnh cha n s chu lc hp dn ca cc
phn t k cn lm gim i tc dng lc va p
vo thnh bnh.

H Th Cm Hoi, PhD

45

H Th Cm Hoi, PhD

46

HE THONG TUAN HOAN

S BIEN OI TUAN HOAN CAC TNH CHAT


CUA CAC NGUYEN TO HOA HOC

V sao phai sap xep cac nguyen to theo


he thong?
De nh
 nh hng cho viec nghien cu cac
nguyen to
 Tao ieu kien cho viec phat hien va
ieu che cac nguyen to mi.


HC - A

Cac cach sap xep


1866 :
Newlands xep theo bo
tam
 1896 :
Lothar Meyer,
Dmitri Mendeleev
xep theo hang, cot


HC - A

Cach sap xep cua Mendeleev


Theo th t tang dan cua khoi lng
nguyen t

HC - A

Danh 4 cho trong cho 4 nguyen to cha c phat hien:


44, 68, 72, & 100
HC - A

HC - A

Mot so ngoai le
Ar (AW=39.948) ng trc
K (AW =39.0983)
Co (AW=58.9332) ng trc
Ni (AW=58.69)

HC - A

Giai thch cac ngoai le


Moseley, Henry Gwyn Jeffreys
18871915, nha vat ly ngi Anh.
Nghien cu tia X
Tm ra s lien he gia ien tch hat nhan va tnh chat
cac nguyen to.
Giai quyet c nhng vng mac cua nh luat tuan
hoan Mendeleev.

HC - A

nh luat tuan hoan mi


Cac nguyen to c sap xep th t tang
dan cua n v ien tch hat nhan

HC - A

He THong Tuan Hoan


IA
1
1

II A

III B

IV B

VB

VI B

VII B

VIII B

IB

II B

III A

IV A

VA

VI A

VII A
1

VIII A
2

He

1.008

1.008

4.0026
10

Li

Be

Ne

6.939

9.0122

10.811

12.011

14.007

15.999

18.998

20.183

11

12

13

14

15

16

17

18

Na

Mg

Al

Si

Cl

Ar

22.99

24.312

26.982

28.086

30.974

32.064

35.453

39.948

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

39.102

40.08

44.956

47.89

50.942

51.996

54.938

55.847

58.932

58.71

63.54

65.37

69.72

72.59

74.922

78.96

79.909

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

Rb

Sr

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

Xe

85.468

87.62

88.906

91.224

92.906

95.94

* 98

101.07

102.91

106.42

107.9

112.41

114.82

118.71

121.75

127.61

126.9

131.29

55

56

57

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Cs

Ba

**La

Hf

Ta

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

132.91

137.33

138.91

178.49

180.95

183.85

186.21

190.2

192.22

195.08

196.97

200.29

204.38

207.2

208.98

* 209

* 210

* 222

87

88

89

104

105

106

107

108

109

110

111

112

Ra ***Ac Rf

Ha

Sg

Ns

Hs

Mt

* 262

* 263

* 262

* 265

* 268

Fr
* 223

226.03 227.03

* 261

* Designates that **Lanthanum


all isotopes are
radioactive

Series
*** Actinium
Series

HC - A

114

116

118

Uuh

Uuo

*285
*289
Based on symbols used by ACS
66
67
68
69

S.M.Condren 1999

Uun Uuu Unb


* 269

* 272

* 277

83.8

Uuq

*293

58

59

60

61

62

63

64

65

70

71

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

140.12

140.91

144.24

* 145

150.36

151.96

157.25

158.93

162.51

164.93

167.26

168.93

173.04

174.97

90

91

92

93

94

95

96

97

98

99

100

101

102

103

Th

Pa

Np

Pu

Am

Cm

Bk

Cf

Es

Fm

Md

No

Lr

232.04

231.04

238.03

237.05

* 244

* 243

* 247

* 247

* 251

* 252

* 257

* 258

* 259

* 260

 Hang

ngang :chu ky
 Co 7 chu ky, chu ky 7 cha ay u

HC - A

1
2
3
4
5
6
7
 Cac

nguyen to trong cung chu ky co


cung so lp vo electron.

HC - A

 Cot

doc : Nhom
 Cac nguyen to trong cung nhom co
tnh chat tng t.
 Co cau hnh electron tng t

HC - A

Cac nguyen to nhom A co so electron hoa


8A
tr = so electron lp vo ngoai cung = so th
1A
0
t nhom
2A
3A 4A 5A 6A 7A


HC - A

Cac nguyen to nhom B (cac nguyen to chuyen tiep)


co so electron hoa tr = so electron lp vo ngoai
cung + so electron phan lp d ke can = so th t
nhom.
Lu y:
nhom 8B gom 3 cot (ng vi so
electron hoa tr = 8, 9, va 10)

28 nguyen to f ( ho Lanthanide va actinide


) thuoc nhom 3B

HC - A

 Nhom

1A : kim loai Kiem


 Nhom 2A: Kim loai Kiem tho

HC - A

 Nhom

7A: nhom Halogen


 Nhom 8A: (nhom 0) kh tr

HC - A

H
Li

1
3

Na
11
K
19
Rb
37
Cs
55
Fr
87
HC - A

1s1
1s22s1
1s22s22p63s1
1s22s22p63s23p64s1
1s22s22p63s23p64s23d104p65s1
1s22s22p63s23p64s23d104p65s24d10
5p66s1
1s22s22p63s23p64s23d104p65s24d105
p66s24f145d106p67s1
:

1s2 He 2
1s22s22p6

Ne
10

1s22s22p63s23p6 Ar18
1s22s22p63s23p64s23d104p6 Kr

36

1s22s22p63s23p64s23d104p65s24d105p Xe
6 54
Rn

1s22s22p63s23p64s23d104p65s24d10 86
:
5p66s24f145d10
6p6

HC - A

Cac nguyen to S

s1
s2

HC - A

 Electron

ang c ien vao vao


phan lp S.
 Kim loai kiem s1
 Kim loai kiem tho s2
 Lu y trng hp ac biet cua He
(thuoc nhom kh tr)

Kim loai chuyen tiep nguyen to d

d1 d2 d3

s1
d5

s1
d5 d6 d7 d8 d10 d10

HC - A

Nguyen to P

HC - A

p1 p2

p3

p4

p5

p6

Nguyen to F

f1 f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14

HC - A

Viet tat cau hnh electron da


vao he thong tuan hoan

Nguyen tac
 Viet

ky hieu cua nguyen to kh tr gan


nhat [trong ngoac vuong].
 Bo sung cac electron con lai.
 V du:
 Cau hnh cua Al.
 1s22s22p63s23p1
 Ne co cau hnh 1s22s22p6
 Vay Al : [Ne] 3s23p1
:

HC - A

V du
= 1s22s22p63s23p64s23d104p2
 Ge = [Ar] 4s23d104p2
 Hf=1s22s22p63s23p64s23d104p65s2
4d105p66s24f145d2
2 14 2
 Hf=[Xe]6s 4f 5d
 Ge

HC - A

Vd: cau hnh cua Sn (Z=50)


Sn- 50 electrons
Kh tr gan
nhat Kr
Kr co 36 electron
Can them 5s2
Roi 4d10
Cuoi cung la 5p2

[ Kr ] 5s2 4d10 5p2


HC - A

S BIEN OI TUAN HOAN CAC TNH CHAT


CUA CAC NGUYEN TO HOA HOC

Cac tnh chat can lu y


 Ban

knh nguyen t
 Nang lng ion hoa
 Ai lc electron
 o am ien

HC - A

Ban knh nguyen t


 Kho

khan: lam the nao e o kch


thc cua nguyen t?
am may electron khong co gii han
xac nh.

HC - A

Ban knh
Ban knh nguyen t = khoang cach gia 2 hat
nhan.
:

HC - A

Cac loai ban knh


 Ban

knh kim loai


 Ban knh Cong hoa tr
 Ban knh ion
 Ban knh Van Der Wall
 So

lieu ban knh co the tra cu t cac so


tay hoa hoc.

HC - A

Quy luat bien oi


 Hai

yeu to anh hng.


 Mc nang lng
Electron phan lp co nang lng cang
cao th cang xa hat nhan .
 ien tch hat nhan Z (so proton)
Z cang ln, tac dung hut electron cua
hat nhan cang manh.

HC - A

 So

NHOM

phan lp tang
(n tang)
 Z tang
 Anh hng cua n
manh hn cua Z
nen ban knh
tang.

H
Li
Na
K

Rb
HC - A

Chu ky
 i

t au en cuoi chu ky.


Cung so phan lp (n khong oi).
Z tang.
Ban knh giam.

Na

Mg

Al

Si

S Cl Ar

HC - A

HC - A

Rb
K

Ban knh (nm)

Na
Li
Kr
Ar
Ne
H

10

HC - A

HC - A

Nang lng ion hoa


 Nang

lng can cung cap e bt


electron ra khoi nguyen t hay ion
trang thai kh.
 Bt 1 electron lam tang ien tch len 1
n v.
 Nang lng dung e bt electron au
tien : nang lng ion hoa th nhat.

HC - A

Nang lng ion hoa


 Nang

lng e bt electron th 2 (t ion


mang ien tch +1): nang lng ion hoa
th 2 .

I3> I2 > I1

HC - A

Nt
H
He
Li
Be
B
C
N
O
F
Ne

I1

1312
2731
520
900
800
1086
1402
1314
1681
2080

I2
5247
7297
1757
2430
2352
2857
3391
3375
3963

11810
14840
3569
4619
4577
5301
6045
6276
:

HC - A

Nt
H
He
Li
Be
B
C
N
O
F
Ne
HC - A

I3

I1

I2

1312
2731
520
900
800
1086
1402
1314
1681
2080

5247
7297
1757
2430
2352
2857
3391
3375
3963

I3
11810
14840
3569
4619
4577
5301
6045
6276
:

Cac yeu to anh hng


Z

: Z tang I tang.
 n : n tang I giam
 Cac cau hnh bao hoa va ban bao hoa co
nang lng thap, e at ti cac cau hnh
nay ch can I nho.
 Hieu ng chan

HC - A

 Cac

Hieu ng chan

electron ben trong


co tac dung che chan
cac electron ben ngoai
khoi tac dung cua hat
nhan.
 Hieu ng chan cang
ln, I cang nho

HC - A

Quy luat bien oi trong nhom

 I1

giam khi i t tren xuong di


trong mot phan nhom
n tang
Hieu ng chan tang.

HC - A

Quy luat bien oi trong chu ky


 Cac

nguyen to trong cung chu ky co :

n giong nhau.
Cung hieu ng chan.
Z tang t au en cuoi chu ky
I1 tang t au en cuoi chu ky.

 Lu

hoa.

HC - A

y ngoai le cho cac cau hnh ban bao

He

va H.
 Cung hieu ng chan
 He co Z ln hn
I1

 He

Z
:

HC - A

He

Li & H
 Li co hieu ng chan
ln hn
 N ln hn
 Vt troi anh hng
cua Z

I1

Li

Z
HC - A

He

Be & Li
 Cung hieu ng chan
 Be co Z ln hn
I1

Be

Li

Z
:

HC - A

He

B va Be
 Cung hieu ng chan
 B co Z ln hn
 B mat 1 electron at
cau hnh ben 2s2

I1

Be
B
Li

Z
HC - A

I1

He

Be

Li

Z
:

HC - A

He

I1

Be

Li

Z
HC - A

He

I1

C O

Be

Li

O

co I1 nho hn
cua N v O mat 1
electron at cau
hnh ban bao hoa
2p3

Z
:

HC - A

He

I1

N F

C O

Be

Li

Z
HC - A

Ne

He

I1

N F

C O

Be

Li

 Ne

va He
 Ne : hieu ng
chan manh hn
 N ln hn

Z
:

HC - A

Ne

He

I1

N F

C O

Be

Li

B
Na

Z
HC - A

I1

Z
HC - A

HC - A

V du
Sap xep cac nguyen to sau theo th t
I1 tang dan:
C, K, Mg, Na, Ne, Si
K < Na < Mg < Si < C < Ne

HC - A

Ai l c electron
Nang lng cua qua trnh them 1 electron vao mot
nguyen t trung hoa the kh.
Cl(g) + e

Cl(g)

E = -349 kJ/mol

E co gia tr cang am chng to nguyen t cang de


nhan electron
E dng the hien qua trnh nhan electron khong
c thuan li.
Ne(g) + e
HC - A

Ne(g)

E = 40 kJ/mol
:

Quy luat bien oi


tang (gia tr E cang am) khi i t
au en cuoi chu ky
 A giam t tren xuong di trong mot
phan nhom
 Lu y mot so trng hp ngoai le: khi
nguyen t co cau hnh electron qua ben,
kha nang nhan them electron la kho xa
ra E dng
A

HC - A

Ai lc electron

HC - A

S hnh thanh ion


 Cation

(ion dng) hnh thanh khi


nguyen t trung hoa b mat electron.
 Cation cua 1 nguyen to se nho hn
nguyen t trung hoa cua nguyen to o.

HC - A

S hnh thanh ion


 Anion

(ion am) hnh thanh khi nguyen


t nhan elctron
 Anion co kch thc ln hn nguyen t
trung hoa

HC - A

HC - A

Ion ang ien t


 Co

cung so elctron
 Cung cau hnh elcrton
 Kch thc phu thuoc vao Z
 V du:
 Al+3 Mg+2 Na+1 Ne F-1 O-2 va N-3
 Cung co 10 electron
 Cung cau hnh 1s12s22p6

HC - A

Kch thc ion ang ien t


Z

Al+3

ln th r nho.

Na+1

Ne

F-1

N-3

O-2

Mg+2
:

HC - A

o am ien

o am ien
 The

hien kha nang hut cap electron lien


ket cua mot nguyen t
 Lu y khong nham lan vi ai lc
electron
 o am ien t le thuan vi ai lc
electron.

HC - A

Quy luat bien oi


 Giam

theo nhom
 Tang theo chu ky
 Thang

o am ien hay s dung la thang


Pauling.

HC - A

Phan loai nguyen to


Kim loai: I nho, de nhng electron
Phi kim: A ln , de nhan electron.

HC - A

Nang lng ion hoa , o am ien


Ai lc electron TANG

HC - A

Ban knh nguyen t

HC - A

V du 1


HC - A

Sap xep cac nguen t sau theo th t


ban knh tang dan
a) Sr < Rb < Ca
b) Ca < Sr < Rb .
c) Ca < Rb < Sr
d) Ca < Sr = Rb

V du 2
Xep theo chieu tang dan cua ai lc
electron
a) P < S < Cl
b) Sr < Ca < Mg
c) Li < Na < K
d) Br < Cl < Se
e) As < Sn < Ge

HC - A

Example 4


HC - A

Cau hnh nao la cua Sn


a) [Kr]5s24d105p2
b) [Xe] 5s24d105p2
c) [Kr] 5s25d105p2
d) [Kr] 5s24d105p3
e) [Kr] 5s24d105p1

V du 4


Xep theo chieu giam dan cua tnh kim


loai?
a) Sr > Rb > Ca.
b) Ca > Sr = Rb
c) Rb > Sr > Ca
d) Sr > Rb > Ca
e) Ca > Sr > Rb

HC - A

V du 5
au la cau hnh trang thai nen cua mot
nguyen to?
a) 1s22s22p63s23p64s1
b) 1s22s22d63s23p64s23d7
c) 1s22s22p63s23p63d3
d) 1s22s22p83s23p8
e) 1s22s22p63s23p44s23d7

HC - A

Example 7


HC - A

Cau hnh nao khong chnh xac?


a) Cd = [Kr]4d10
b) Ra = [Rn]7s2
c) Li = [He]2s1
d) Pb = [Xe]6s24f145d106p2
e) Se = [Ar]4s23d104p4

NG HA HC
Chemical Kinetics

Ha i cng A2

Chng 3

NG HA HC
ng ha hc tm hiu xem phn ng xy ra
nhanh chm ra sao
C 4 yu t quan trng nh hng ln vn tc:
Nng tc cht
nhit
hat ca xc tc
tnh cht b mt.
Mc ch: Tm hiu cc phn ng ha hc
mc phn t nhm m hnh ho cc qu
trnh trong t nhin.
Ha i cng A2

Chng 3

Vn tc phn ng
Reaction Rates
Vn tc ca mt phn ng c o bng bin
thin ca nng theo thi gian.
Xem phn ng
AB
(nng ca tc cht
A)
Vntc = --------------------------------- (thi gian)
y l biu thc ca vn tc trung bnh
Ha i cng A2

Chng 3

Chng 3

Chemical Kinetics
Reaction Rates

Ha i cng A2

Vn tc trung bnh
Ti t = 0 (time zero): 1.00 mol A (100 red
spheres); 0.0 mol B
Ti t = 20 min: 0.54 mol A, 0.46 mol B.
Ti t = 40 min: 0.30 mol A, 0.70 mol B.
Vy:

(moles of B)
t
(moles of B at t = 10) (moles of B at t = 0)
=
10 min - 0 min
0.26 mol - 0 mol
=
= 0.026 mol/min
10 min - 0 min
Vtb =

Ha i cng A2

Chng 3

Chng 3

Chemical Kinetics
Reaction Rates

Ha i cng A2

Vn tc trung bnh
Rates in Terms of Concentrations
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Ha i cng A2

Chng 3

Vn tc tc thi (instantaneous rate)


 Phn ng chm dn theo thi gian (the
average rate decreases with time).
 Dng ng tip tuyn ca ng cong
biu din vn tc theo thi gian. D dc
ca tip tuyncho ta vn tc tc thi
(instantaneous rate) ca phn ng ti
thi im
 Du ca vn tc ph thuc h s gc ca
ng tip tuyn
 T nay khi ni ti vn tc l ni ti vn
tc tc thi
Ha i cng A2

Chng 3

Vn tc tc thi (instantaneous rate)


Rates in Terms of Concentrations

Ha i cng A2

Chng 3

Chemical Kinetics
Reaction Rates and Stoichiometry
For the reaction
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
we know
[C4 H 9Cl ] [C4 H 9OH ]
Rate =
=
t
t
In general for
aA + bB cC + dD

Rate =
Ha i cng A2

1 [A ]
1 [B ] 1 [C] 1 [D]
=
=
=
a t
b t
c t
d t
Chng 3

10

Biu thc vn tc phn ng

Vi nhng nng u khc nhau, ngi ta


nhn thy rng vn tc phn ng tng khi
nng tng:
NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)

Ha i cng A2

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11

Biu thc vn tc phn ng


NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)
 Khi nng [NH4+] tng 2 ln, nng
[NO2-] khng i th vn tc phn ng tng 2
ln
 Khi n
nng
ng
[NO2-] tng 2 lln,
n, n
nng
ng

[NH4+] khng i th vn tc phn ng cng


tng 2 ln
vn tc [NH4+][NO2-].
Biu thc vn tc phn ng
vn tc = k[NH4+][ NO2-].
k l hng s tc ca phn ng
Ha i cng A2

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12

Bc ca phn ng
Mt biu thc vn tc c dng

vn tc = k[reactant 1]m[reactant 2]n


 Bc phn ng c nh ngha l tng s m
ca cc nng
 Phn ng trn c gi l c bc m theo
reactant 1, bc n theo reactant 2 v bc tng
cng l m+n
 Biu thc vn tc l mt c trng c xc
nh t thc nghim ca mt phn ng; N
khng th c tnh ton da trn h s t
lng ca phng trnh ho hc.
Ha i cng A2

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13

S bin i ca vn tc theo nng


Dng vn tc u xc nh biu thc vn tc
Mt phn ng c bc zero theo mt tc cht nu
thay i nng tc cht khng nh hng
ln vn tc.
Mt phn ng l bc nht nu tng gp i
nng vn tc tng gp i.
Mt phn ng l bc hai nu tng gp i nng
vn tc tng 22 ln.
Mt phn ng l bc n nu tng gp i nng
vn tc tng 2n ln.
Lu : hng s vn tc khng ph thuc bc
phn ng
Ha i cng A2

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14

The Change of Concentration with Time


Phn ng bc nht n gin
Ta c th chuyn biu thc vn tc thnh
phng trnh biu din nng theo thi gian.
i vi phn ng bc nht, vn tc tng gp i
khi nng tng gp i.

ln[A ]t = kt + ln[A ]0
ng ln[A]t theo t l mt ng thng vi
dc -k v tung gc ln[A]0.
Ha i cng A2

Chng 3

15

Phn ng bc nht n gin

ln[A ]t = kt + ln[A ]0

Ha i cng A2

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16

Bn sinh phn ng (Half(Half-Life) t1/2


Half-life t1/2 l thi gian nng tc cht gim
cn mt na so vi ban u.
Tc l half life, t1/2 , l thi gian nng tc
cht A gim t [A]0 xung [A]0.
Biu thc ca t1/2

ln 1
t1 =
2

2 = 0.693

 half life, t1/2 , khng ph thuc nng u ca


tc cht [A]o
Ha i cng A2

Chng 3

17

Bn sinh phn ng (Half-Life) t1/2

Ha i cng A2

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18

The Change of Concentration with Time


Phn ng bc hai n gin
Cho phn ng bc hai vi ch mt tc cht A

1
1
= kt +
[A]t
[A]0
ng biu din 1/[A]t theo t l mt ng
thng vi dc k v tung gc 1/[A]0
ng biu din ca ln[A]t theo t khng phi l
ng thng.

Ha i cng A2

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19

Phn ng bc hai n gin

Ha i cng A2

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20

Bn sinh phn ng (Half-Life) t1/2


 Bn sinh phn ng (Half-Life) t1/2 ph thuc
nng u ca tc cht [A]o

t1 =
2

1
k [A ]0

Mt phn ng c biu thc vn tc dng:


rate = k[A][B],
l phn ng c bc chung l bc hai nhng bc
nht theo A v B.
Ha i cng A2

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21

S bin i ca vn tc theo nhit


Hu ht cc phn ng u xy ra nhanh hn khi
tng nhit . (VD. thc phm b h khi khng
c tr lnh.)
Do trong biu thc vn tc khng cha i
lng c trng cho nhit , i lng ny
phi c cha trong k.
Nhit tng lm vn tc phn ng tng do k
tng.

Ha i cng A2

Chng 3

22

nhit v vn tc

Ha i cng A2

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23

nhit v vn tc
Xt phn ng bc nht:
CH3NC CH3CN.
 Khi nhit tng t 190 C ln 250 C, hng s
vn tc tng t 2.52 10-5 s-1 ln 3.16 10-3 s-1.
Ti sao nh hng ca nhit li ln nh
vy?

Ha i cng A2

Chng 3

24

Thuyt va chm ((The


The Collision Model)
T nhng quan st cho thy vn tc phn ng
ph thuc vo nng v nhit , ngi ta
a ra l thuyt nhm gii thch nhng kt qu
quan st ny.
The collision model:
phn ng xy ra, cc phn t phi va chm
mnh vi nhau
S ln va chm cng nhiu, vn tc phn ng
cng ln

Ha i cng A2

Chng 3

25

Chng 3

26

The Collision Model

Ha i cng A2

The Collision Model


S phn t hin din cng nhiu, kh nng va
chm cng ln, vn tc cng ln.
Nhit cng cao, cc phn t cng s hu
nhiu nng lng, vn tc cng ln.
Lu : Khng phi mi va chm u dn n
phn ng. Thc s ch mt phn nh s va
chm dn n s to thnh sn phm.
phn ng xy ra, cc phn t phi va chm
ng hng vi nng lng ln mi to
thnh sn phm.
Ha i cng A2

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27

Nng lng hat ha (Activation Energy)


Theo Arrhenius: Cc phn t phi s hu mt
nng lng ti thiu no th phn ng mi
xy ra. Ti sao? V:
to thnh sn phm, phi c qu trnh t
ni xy ra tc cht.
Qu trnh t ni cn nng lng
Nng lng hat ha Ea l nng lng ti thiu
khi mo mt phn ng ha hc.

Ha i cng A2

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28

Activation Energy

Ha i cng A2

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29

Activation Energy
Xem qu trnh sp xp ni ca acetonitrile:
H3C N C

H3C

N
C

H3C C N

 Trong H3C-N
C, ni C-N
C bin dng cho n khi ni
C-N b gy v phn N
C gn ngc li vo phn H3C.
Dng cu trc ny gi l phc cht hat ng (activated
complex) hay trng thi chuyn tip (transition state).
 Nng lng cn thit lm bin dng v b gy ni
trn chnh l nng lng hat ha (activation energy)
Ea.
 Khi ni C-N b gy, phn N
C c kh nng tip tc xoay
to nn ni mi C-C
N.
Ha i cng A2

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30

Activation Energy

Ha i cng A2

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31

Activation Energy
S thay i nng lng ca phn ng l s chnh lch
nng lng gia CH3NC v CH3CN.
Nng lng hot haThe activation energy is the
difference in energy between reactants, CH3NC and
transition state.
The rate depends on Ea.
Notice that if a forward reaction is exothermic
(CH3NC CH3CN), then the reverse reaction is
endothermic (CH3CN CH3NC).

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32

Temperature and Rate


Activation Energy
Consider the reaction between Cl and NOCl:
If the Cl collides with the Cl of NOCl then the products are
Cl2 and NO.
If the Cl collided with the O of NOCl then no products are
formed.

We need to quantify this effect.

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33

Temperature and Rate


Activation Energy

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34

Temperature and Rate


The Arrhenius Equation
Arrhenius discovered most reaction-rate data obeyed
the Arrhenius equation:
Ea
RT
k = Ae
k is the rate constant, Ea is the activation energy, R is the gas
constant (8.314 J/K-mol) and T is the temperature in K.
A is called the frequency factor.
A is a measure of the probability of a favorable collision.
Both A and Ea are specific to a given reaction.

If we have a lot of data, we can determine Ea and A


graphically by rearranging the Arrhenius equation:
Ha i cng A2

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35

Temperature and Rate


The Arrhenius Equation
If we have a lot of data, we can determine Ea and A
graphically by rearranging the Arrhenius equation:

E
ln k = a + ln A
RT
If we do not have a lot of data, then we can use

k1 Ea 1 1
ln

=
k2
R T2 T1

Ha i cng A2

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36

Reaction Mechanisms
The balanced chemical equation provides information
about the beginning and end of reaction.
The reaction mechanism gives the path of the
reaction.
Mechanisms provide a very detailed picture of which
bonds are broken and formed during the course of a
reaction.

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37

Reaction Mechanisms
Elementary Steps
Elementary step: any process that occurs in a single
step.
Molecularity: the number of molecules present in an
elementary step.
Unimolecular: one molecule in the elementary step,
Bimolecular: two molecules in the elementary step, and
Termolecular: three molecules in the elementary step.

It is not common to see termolecular processes


(statistically improbable).

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38

Reaction Mechanisms
Elementary Steps
Elementary steps must add to give the balanced
chemical equation.
Intermediate: a species which appears in an
elementary step which is not a reactant or product.

Rate Laws of Elementary Steps


The rate law of an elementary step is determined by
its molecularity:
Unimolecular processes are first order,
Bimolecular processes are second order, and
Termolecular processes are third order.
Ha i cng A2

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39

Reaction Mechanisms
Rate Laws of Multistep Mechanisms
Rate-determining step: is the slowest of the
elementary steps.
Therefore, the rate-determining step governs the
overall rate law for the reaction.

Mechanisms with an Initial Fast Step


It is possible for an intermediate to be a reactant.
Consider
2NO(g) + Br2(g) 2NOBr(g)

Ha i cng A2

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40

Reaction Mechanisms
Mechanisms with an Initial Fast Step
2NO(g) + Br2(g) 2NOBr(g)
The experimentally determined rate law is
Rate = k[NO]2[Br2]
Consider the following mechanism
k1
NOBr2(g)
Step 1: NO(g) + Br2(g)
k-1

Step 2: NOBr2(g) + NO(g)

k2

(fast)

2NOBr(g) (slow)

for which the rate law is (based on Step 2):


Ha i cng A2

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41

Reaction Mechanisms
Mechanisms with an Initial Fast Step
The rate law is (based on Step 2):
Rate = k2[NOBr2][NO]
The rate law should not depend on the concentration
of an intermediate because intermediates are usually
unstable.
Assume NOBr2 is unstable, so we express the
concentration of NOBr2 in terms of NOBr and Br2
assuming there is an equilibrium in step 1 we have

[NOBr2 ] =
Ha i cng A2

k1
[NO][Br2 ]
k 1
Chng 3

42

Reaction Mechanisms
Mechanisms with an Initial Fast Step
By definition of equilibrium:
k1[NO][Br2] = k-1[NOBr2]
Therefore, the overall rate law becomes

k
Rate = k2 1 [NO]2 [Br2 ]
k 1
Note the final rate law is consistent with the
experimentally observed rate law.

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43

Catalysis
A catalyst changes the rate of a chemical reaction.
There are two types of catalyst:
homogeneous, and
heterogeneous.

Chlorine atoms are catalysts for the destruction of


ozone.

Homogeneous Catalysis
The catalyst and reaction is in one phase.
Hydrogen peroxide decomposes very slowly:
2H2O2(aq) 2H2O(l) + O2(g).
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44

Catalysis
Homogeneous Catalysis
2H2O2(aq) 2H2O(l) + O2(g).
In the presence of the bromide ion, the decomposition
occurs rapidly:

2Br-(aq) + H2O2(aq) + 2H+(aq) Br2(aq) + 2H2O(l).


Br2(aq) is brown.
Br2(aq) + H2O2(aq) 2Br-(aq) + 2H+(aq) + O2(g).
Br- is a catalyst because it can be recovered at the end of the
reaction.

Generally, catalysts operate by lowering the activation


energy for a reaction.
Ha i cng A2

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45

Catalysis
Homogeneous Catalysis

Ha i cng A2

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46

Catalysis
Homogeneous Catalysis
Catalysts can operate by increasing the number of
effective collisions.
That is, from the Arrhenius equation: catalysts
increase k be increasing A or decreasing Ea.
A catalyst may add intermediates to the reaction.
Example: In the presence of Br-, Br2(aq) is generated
as an intermediate in the decomposition of H2O2.
When a catalyst adds an intermediate, the activation
energies for both steps must be lower than the
activation energy for the uncatalyzed reaction.
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47

Catalysis
Heterogeneous Catalysis
The catalyst is in a different phase than the reactants
and products.
Typical example: solid catalyst, gaseous reactants and
products (catalytic converters in cars).
Most industrial catalysts are heterogeneous.
First step is adsorption (the binding of reactant
molecules to the catalyst surface).
Adsorbed species (atoms or ions) are very reactive.
Molecules are adsorbed onto active sites (red spheres)
on the catalyst surface.
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48

Catalysis
Heterogeneous Catalysis

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49

Catalysis
Heterogeneous Catalysis
Consider the hydrogenation of ethylene:
C2H4(g) + H2(g) C2H6(g), H = -136 kJ/mol.
The reaction is slow in the absence of a catalyst.
In the presence of a metal catalyst (Ni, Pt or Pd) the
reaction occurs quickly at room temperature.
First the ethylene and hydrogen molecules are adsorbed
onto active sites on the metal surface.
The H-H bond breaks and the H atoms migrate about the
metal surface.

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50

Catalysis
Heterogeneous Catalysis
Consider the hydrogenation of ethylene:
C2H4(g) + H2(g) C2H6(g), H = -136 kJ/mol.
When an H atom collides with an ethylene molecule on the
surface, the C-C bond breaks and a C-H bond forms.
When C2H6 forms it desorbs from the surface.
When ethylene and hydrogen are adsorbed onto a surface,
less energy is required to break the bonds and the activation
energy for the reaction is lowered.

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51

Catalysis
Enzymes
Enzymes are biological catalysts.
Most enzymes are protein molecules with large
molecular masses (10,000 to 106 amu).
Enzymes have very specific shapes.
Most enzymes catalyze very specific reactions.
Substrates undergo reaction at the active site of an
enzyme.
A substrate locks into an enzyme and a fast reaction
occurs.
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52

Catalysis
Enzymes

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53

Catalysis
Enzymes
The products then move away from the enzyme.
Only substrates that fit into the enzyme lock can be
involved in the reaction.
If a molecule binds tightly to an enzyme so that
another substrate cannot displace it, then the active
site is blocked and the catalyst is inhibited (enzyme
inhibitors).
The number of events (turnover number) catalyzed is
large for enzymes (103 - 107 per second).

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54

Catalysis
Nitrogen Fixation and Nitrogenase
Nitrogen gas cannot be used in the soil for plants or
animals.
Nitrogen compounds, NO3, NO2-, and NO3- are used in
the soil.
The conversion between N2 and NH3 is a process with
a high activation energy (the N
N triple bond needs to
be broken).
An enzyme, nitrogenase, in bacteria which live in root
nodules of legumes, clover and alfalfa, catalyses the
reduction of nitrogen to ammonia.
Ha i cng A2

Chng 3

55

Catalysis
Nitrogen Fixation and Nitrogenase

Ha i cng A2

Chng 3

56

Catalysis
Nitrogen Fixation and Nitrogenase
The fixed nitrogen (NO3, NO2-, and NO3-) is consumed
by plants and then eaten by animals.
Animal waste and dead plants are attacked by
bacteria that break down the fixed nitrogen and
produce N2 gas for the atmosphere.

Ha i cng A2

Chng 3

57

Chemical Kinetics

End of Chapter 14
Ha i cng A2

Chng 3

58

bt1

LIEN KET HOA HOC

HC - A

Slide 1
bt1

bat tai, 3/28/2004

V sao nghien cu Lien ket hoa hoc


Vat chat tao thanh do cac nguyen t lien ket
vi nhau.
Hieu c ban chat lien ket se giup hieu c
tnh chat cua cac chat

HC - A

V sao cac nguyen t lai lien ket vi nhau?


e at ti trang thai ben vng cua he thong.

HC - A

Cac nguyen t lien ket vi nhau nh


the nao?
Do khong the quan sat trc tiep cac lien ket hoa
hoc, ta da vao tnh chat cua cac lien ket e xay
dng cac mo hnh (ly thuyet) e bieu dien lien
ket gia cac nguyen t.
Cac ly thuyet c s dung nhieu nhat la:
Thuyet Bat t cua Lewis
Thuyet tng tac cac cap electron (VSEPR)
Thuyet Lien ket Hoa Tr.(VB)
Thuyet Van ao Phan t (MO)

HC - A

Phan loai lien ket hoa hoc


Tuy theo ban chat, lien ket hoa hoc c phan
thanh 3 loai chnh
Lien ket ion
Lien ket cong hoa tr
Lien ket kim loai.

Ban chat va tnh chat cua moi loai lien ket tren c
giai thch bang cac thuyet ve lien ket hoa hoc thch
hp.

HC - A

Lien ket ion


Lien ket ion c coi la he qua cua s tao thanh
cac ion am va dng thong qua viec cho nhan
electron gia cac nguyen t.
c giai thch kha tot qua ly thuyet n gian
cua Lewis.

HC - A

Lien ket Cong Hoa Tr


Lien ket cong hoa tr co ban chat la s dung
chung electron gia cac nguyen t.
Thng c giai thch thong qua thuyet lien
ket hoa tr hoac thuyet van ao phan t.

HC - A

Lien Ket Kim Loai


Lien ket kim loai khong the giai thch thau ao
bang thuyet Lewis cung nh thuyet Lien ket
hoa tr do o thng c giai thch bang thuyet
mien nang lng, thc chat la thuyet van ao
phan t ap dung cho he co khoang 1023 nguyen
t.

HC - A

Cac ly thuyet ve
Lien Ket Hoa Hoc

HC - A

Thuyet Lewis
Electron hoa tr la cac electron nam
trong cac lp vo ngoai cung cha bao
hoa cua cac nguyen t.
Lien ket hoa hoc hnh thanh do cac
nguyen t trao oi hoac s dung chung
cac electron hoa tr
Luat Bat t
Cac nguyen t co xu hng cho,
nhan, hay s dung chung electron e
at ti cau hnh lp vo ngoai cung
ben vng co 8 electron

G.N.Lewis
1875-1946
American Chemist

HC - A

Ky hieu Lewis
Mo ta cac electron hoa tr cua cac nguyen
t.
Hydro:

H
Na

Natri:
Clor:
HC - A

Cl

S hnh thanh lien ket


S hnh thanh NaCl:

Cl

Na+

Cl

Na +

S hnh thanh HCl:

H Cl

Cl

H +

Kim loai nhng electron cho phi kim e tao lien ket ion.
Hai phi kim dung chung electron e tao lien ket Cong Hoa Tr.
HC - A

Hp chat ion
Trong cac hp chat ion, cac ion dng va am sap
xep thanh mot mang li tinh the vng chac. (v
du : NaCl)

HC - A

Lien ket ion


Lien ket ion hnh thanh do s tng tac tnh ien
gia cac ion trai dau.
ien tch cua hai
ion la Q1 va Q2:

Q2

Q1

d
Nang lng tng tac:
HC - A

Ban Knh Ion

HC - A

Q1Q2
d

Nang lng mang tinh the


La ai lng the hien o ben cua lien ket ion.
c nh ngha la s thay oi entalpy cua qua trnh
tach 1 mol hp chat ion ra thanh cac ion rieng le
NaCl(s) Na+(g) + Cl-(g)

DH = 788 kJ

Nang lng mang ty le thuan vi ien tch ion va ty le


nghch vi kch thc ion.
KCl(s) K+(g) + Cl-(g)

DH = 701 kJ

MgCl2(s) Mg+2(g) + 2 Cl(g) DH = 3795 kJ


HC - A

Chu trnh Born-Haber


Nang lng mang tinh the co th c tnh da
theo nh luat Hess theo cac bc sau.
Na+(k) + e- + Cl(k)

E(Cl)
I1(Na)

Na+(k) + Cl-(k)

Na(k) + Cl(k)
Hf(Cl,k) Na(k) + Cl (k)
2
Hf(Na,k) Na(r) + Cl2(k)
Hf(NaCl,r)
HC - A

NaCl(r)

Nang lng
mang

Nang lng mang


Sap xep cac chat sau theo th t nang lng
mang tang dan:
Q1Q2

E
701 kJ
KCl
d
910 kJ
Cl
NaF
K+

MgO

3795 kJ

KBr

671 kJ

NaCl
HC - A

d
K+

Br

788 kJ
d

Nang lng mang cua mot so hp chat ion

HC - A

Lien ket Cong Hoa Tr

Trong lien ket ion, mot nguyen t nhng han


electron (tao ion dng) mot nguyen t nhan han
electron (tao ion am).
Khi hai nguyen t tng t nhau hnh thanh lien
ket, khong nguyen t nao muon nhng hay nhan
han electron.
Chung dung chung cap electron e at cau hnh
ben 8 electron.
Moi cap electron dung chung tao thanh mot lien
ket.

HC - A

Cong thc Lewis


Mo ta lien ket trong cac hp chat cong hoa tr.
Moi nguyen t phai co 8 electron lp vo ngoai
cung (tr H co 2 electron).
H + H H H hay H H
Cl
Cl

HC - A

Cl
Cl

Electron khong lien ket

Electron
lien ket

Cl
+ Cl

Cl2:

H 2:

Cong thc Lewis

H F

HF:

hay H F

H O
H

H2O:

hay H O H

hay H N H
H

H C
H

H
hay H C H
H

HC - A

CH4:

H N H

NH3:

Lien ket n, lien ket ba

N 2:

N N

O
=O

O 2:

So cap electron dung chung c goi la


Bac lien ket .

HC - A

Lien ket Cong Hoa Tr co cc


Khi cap electron c phan bo eu gia hai
nguyen t : lien ket khong phan cc

H 2,
Cl2:
Khi co s phan bo khong ong eu: lien ket
cong hoa tr co cc
HCl:
HC - A

o Am ien
o phan cc cua lien ket c
xac nh da vao s khac biet
O AM IEN gia hai nguyen
t tao lien ket.
190194

Nobel Hoa hoc : 1954


Nobel Hoa Bnh : 1962

HC - A

Thang o am ien thong dung


do Pauling e ngh.

Thang o am ien Pauling

HC - A

o phan cc (% ion) cua lien ket


% ion = (gia tr o bang thc nghiem cua moment lng cc X-Y)/ (gia tr tnh toan moment lng cc X+ Y+)
% ion cua lien ket c Pauling xac nh thong qua o chenh lech o am ien cua hai nguyen to :

o chenh
lech o am
ien

% ion cua
lien ket

o chenh
lech o am
ien

% ion cua
lien ket

o chenh
lech o am
ien

% ion cua
lien ket

0.2

1.4

39

2.4

76

0.4

1.6

47

2.6

82

0.6

1.8

55

2.8

86

0.8

15

2.0

63

3.0

89

1.0

22

2.2

70

3.2

92

1.2

30

HC - A

HC - A

Cong thc Lewis


Tnh tong so electron hoa tr cua cac nguyen t.
Ion ien tch n- : cong them n electron hoa tr
Ion ien tch n+ : tr i n electron hoa tr
Phan bo cac nguyen t quanh nguyen t trung tam. (NTTT la
nguyen t co o am ien nho hn, tr H)
Ve cac lien ket n t nguyen t trung tam en cac nguyen
t khac.
Hoan thanh bat t cho cac nguyen t ngoai
at cac electron hoa tr con d vao nguyen t trung tam
Neu nguyen t trung tam cha at bat t, tao lien ket boi
gia nguyen t trung tam vi cac nguyen t ngoai.
HC - A

V du

24 e

14 e

HOCl

H O
Cl

COCl2

Cl
C Cl

26 e

CH3OH

O
Cl
O

ClO3

H C O
H

14 e

HC - A

Dang cong hng


Cong thc Lewis cua O3 co hai dang tng
ng nhau:

O
=O O

O O =O

Thc nghiem cho thay hai lien ket O-O la


tng ng nhau (cung co o dai noi la
0.128 nm
Khi bieu dien cau tao phan t O3 ta phai viet
ong thi 2 cong thc
HC - A

V du
24 e

20 e

O
N O

C 2H 6O

O
=N O

O
N =O

NO3

H
H H
H

H C C O
H H C O
C H

H H
H
H
Methyl ether
Ethyl alcohol

HC - A

V du
C 6H 6

30 e

H
H

HC - A

C
C

H
C
C
H

C
C

C
C

H
C
C
H

C
C

H
H

Cac dang cong hng khong tng


ng
N2O co 3 dang cong hng khong tng ng:
N
NO

N
=N =O

N N O

e xac nh dang cong hng mo ta chnh xac nhat cau


truc N2O ta can xac nh ien tch tren moi nguyen t
HC - A

ien tch tren nguyen t


ien tch = so electron hoa tr cua nguyen t
- so electron khong lien ket
- so electron lien ket

HC - A

-1 +1

0 +1 -1

N N O

N
=N=O

N
NO

N2O:

-2 +1 +1

Dang cong hng thch hp


1. Co cac ien tch nho nhat.
2. Khong co ien tch cung dau tren hai nguyen
t ke can
3. ien tch am nam tren nguyen t co o am
ien cao hn.

-1 +1

0 +1 -1

N N O

N
=N=O

HC - A

Thch hp

Ngoai le cua thuyet Bat t


Trong nhieu trng hp, thuyet Bat t cua Lewis
khong c tuan theo:
Cac phan t co so le electron hoa tr.
Nguyen t trung tam co t hn 8 electron.
Nguyen t trung tam co nhieu hn 8 electron
hoa tr.

HC - A

N
NO

N2O:

-2 +1 +1

So le electron hoa tr

N
=O

Lien ket trong NO phai c giai thch da vao


thuyet Van ao Phan T

HC - A

t hn 8 electron
BeF2
+1 -2 +1

F = Be = F

F Be F

Thch hp

HC - A

t hn 8 electron
+1
-1

BF3:

F
=B F

F
B F

F
B F

0 F

0 F

F
B=F

Thch hp

HC - A

Nhieu hn 8 electron
SO4-2

HC - A

-2

O
S O

O
S O

-2

+2

PF5

Nang lng lien ket CHT


o ben cua lien ket cong hoa tr c o bang nang
lng can thiet e pha v lien ket.
Nang lng lien ket, D(X-Y) la lng nhiet H can e
pha v 1 mol lien ket X-Y the kh.

C + O

C O

D(C-O) = H
= 358 kJ

Khi 1 mol lien ket X-Y c hnh thanh, nang


lng toa ra la D(X-Y).

HC - A

Nang lng lien ket cua mot so lien ket


cong hoa tr

HC - A

Lien he gia nang lng lien ket, o


dai lien ket va bac lien ket
Bac lien ket tang o dai lien ket giam nang
lng lien ket tang
D(C
C) = 348 kJ
D(C=C) = 614 kJ
D(C
C) = 839 kJ

0.154 nm
0.134 nm
0.120 nm

D(C
O) = 358 kJ
D(C=O) = 799 kJ
D(C
O) = 1072 kJ

0.143 nm
0.123 nm
0.113 nm

HC - A

o dai cua mot so lien ket

HC - A

S dung nang lng lien ket e tnh


nhiet phan ng
Hp = D(noi t) D(noi tao).

HC - A

Nhiet phan ng (
HP)
Phan ng gia H2 va O2 tao H2O:

H H + H H + O
=O

H O
H + H O
H

H t noi
H tao noi

= 2 D(HH) + D(O=O)
= 4-D(OH)

Hrxn = 2 D(HH) + D(O=O) - 4 D(OH)


H = D(noi t) - D(noi tao)
HC - A

Nhiet phan ng (
HP)
Tnh nhiet phan ng ot chay 1 mol CH4:
H

H C H + 2 O
=O

H
O=C =O
+
2 H O
H

H = 4 D(CH) + 2 D(O=O)
- 2 D(C=O) - 4 D(OH)
= [ 4(413) + 2(495) - 2(799) - 4(463) ] kJ
= -808 kJ
HC - A

Bai tap ap dung


Viet cong thc Lewis cua CO32-

CO32O

O 2/3
2/3

HC - A

2/3

Bai tap ap dung


Xac nh bac lien ket cua cac lien ket gia nguyen
t N va nguyen t O trong ion NO2-

NO2-

O N O

O N O

1/21/2O
N
O
=
b.o. = 1.5 124 pm
So sanh: N-O
N=O

bac.
136 1.0
115 2.0

HC - A

Bai tap ap dung


Mo ta nao sau ay khong chnh xac cho ban chat
cua lien ket
a)
b)
c)
d)
e)

HC - A

MgS, cong hoa tr co cc


IBr, cong hoa tr co cc
F2, cong hoa tr khong phan cc
NO, cong hoa tr co cc
KF, ion

Bai tap ap dung


Tnh Hp cho phan ng sau
H

H H

H
+H O O H

C C
H

H O C C O H

H H

DHp = SD(noi t) - SD(noi tao)


HP = [D(C=C) + D(O-O)] - [D(C-C) + 2D(C-O)]
= [602 + 146] - [346 + 2(358)]
= -314 kJ
HC - A

Lien ket hoa hoc (tt)


ThuyetTng Tac Cac Cap Electron
Thuyet Lien Ket Hoa Tr
Thuyet Van ao Phan T

HC-A

Hnh dang phan t CHT


Tnh chat cua cac chat CHT phu thuoc vao hnh
dang phan t:
Nhiet o nong chay
Nhiet o soi
Kha nang solvat hoa

HC-A

Cong thc Lewis

Khong cho biet hnh dang cua phan t cua cac hp


chat CHT.
V du:
Phan t CCl4
Thc nghiem cho biet cac goc lien ket ClCCl eu
bang 109o.
Nh vay 4 nguyen t Cl khong cung nam tren mat
phang

HC-A

Phan t CCl4

HC-A

Cac cach bieu dien hnh dang

HC-A

Thuyet tng tac cac cap electron


Valence Shell Electron Pair Repulsion
theory(VSEPR).

Phng phap n gian nhng hieu qua e xac


nh hnh dang phan t CHT.
Nguyen tac:
Cac cap electron quanh nguyen t se sap
xep sao cho s tng tac la nho nhat.
HC-A

Ap dung thuyet VSEPR


Ve cong thc Lewis.
em so v tr co electron quanh nguyen t
Mot cap electron khong lien ket tnh la 1 v tr
Mot lien ket (n, oi hoac Ba) tnh la mot v tr.

Sap xep cac v tr co electron sao cho tng tac


la nho nhat

HC-A

Cac cach sap xep


So v tr Cach xep
2

180

Thang hang
120

Tam Giac
109.5

4
HC-A

T dien

Cac cach sap xep


So v tr Cach xep
5

Lng Thap
Tam Giac

90
120
90
90

Bat dien

HC-A
QuickTime Movie

Cac dang phan t


Phan t
.
CO2

CT Lewis

v tr e cach xep

2 - Thang hang 180

O
=C =O

O
S =O

SO2

goc
Lien ket

3 - Tam Giac

120

3 - Tam Giac

120

O
C O

-2

HC-A

CO3

-2

O
=S O

Cac dang phan t


Phan t
.

CT Lewis

v tr e cach xep

goc
Lien ket

H
CH4

H C H

4 - T dien

109.5

4 - T dien

109.5

H
NH3

H N H
H

HC-A

Cac dang phan t


Phan t
.

CT Lewis

v tr e cach xep

goc
Lien ket

F
S F

Lng thap
5 - Tam giac

SF4

90,
120

F
Xe F

XeF4

HC-A

6 - Bat dien

90

Cac bien dang


Cap electron khong lien ket tng tac manh hn
cac cap electron lien ket.
Lien ket a co tng tac manh hn lien ket n
V du: H2O

H
HC-A

H
104.5

Cac bien dang

H
H C H
H
109.5O

HC-A

H N H
H
107O

O
H
H
104.5O

Cac bien dang

Cl
111.4o

Cl

C O
124.3o

HC-A

Hnh dang phan t

HC-A

Hnh dang phan t

HC-A

Hnh dang phan t

HC-A

Hnh dang phan t

HC-A

Hnh dang phan t

HC-A

Phan t nhieu trung tam


Xac nh s phan bo electron cho tng nguyen t.

Tam giac
H O

H C C O
H

HC2H3O2:

T dien

HC-A

Moment lng cc cua phan t


Khi hai nguyen t co o am ien khac nhau, mat o
ien tch am se cao hn pha nguyen t co o am
ien cao hn. Tao ra moment lng cc cua lien ket.
(Qui c chieu cua moment lng cc hng ve pha
nguyen t am ien hn)

Trong phan t nhieu nguyen t

Moment lng cc cua phan t la tong cac moment


lng cc cua tat ca cac lien ket

HC-A

Moment lng cc cua phan t

HC-A

Moment lng cc cua phan t

HC-A

Moment lng cc cua phan t


F

F B F

BF3:

Tam giac
F

120

Khong phan
cc

CH2O:

Tam giac

H C H

C
H

HC-A

120

H
Phan cc

Moment lng cc cua phan t


Cl

109

Cl
C Cl

T dien

Cl C

Cl

Cl

Khong
phan cc

H C H
H

HC-A

Cl

CH3Cl:

Cl

Cl

CCl4:

Cl

T dien

H C

Phan cc

THUYET LIEN KET HOA TR


Valence Bond Theory

HC-A

Thuyet Lien ket hoa tr


Thuyet Lewis va VSEPR khong giai thch c
o ben cua cac lien ket cong hoa tr.
Thuyet Lien ket hoa tr da tren ket qua cua
c hoc lng t e giai thch s tao thanh lien
ket.

HC-A

Thuyet lien ket hoa tr


Lien ket hoa hoc tao thanh do s xen phu cua
cac orbital cua cac nguyen t.
Cac orbital ch xen phu vi nhau khi:

Hai orbital, moi orbital cha 1 electron


Mot orbital cha 2 electron va 1 orbital trong
(lien ket cho nhan hay lien ket phoi tr)
Co hai kieu xen phu tao thanh hai loai lien ket:
va

HC-A

Lien ket
Lien ket s (sigma) tao thanh do s xen phu oi
xng theo truc cua hai orbital.
S xen phu cua 2 orbital pz trong phan t O2:
E

HC-A

0.08

0.16

0.24

0.32 nm

Lien ket p
Lien ket p (pi) hnh thanh do s xen phu oi xng
theo mat phang
S xen phu cua 2 orbital py trong phan t O2

HC-A

o ben lien ket


Lien ket cang ben khi mc o xen phu cac Orbital
cang ln (mat o nguyen t gia hai hat nhan
la ln nhat)
1. Mc o xen phu phu thuoc vao: hnh dang,
kch thc, nang lng cua cac orbital, hng
xen phu va kieu xen phu gia chung.
2. Cac orbital co nang lng tng ng nhau
se xen phu tot
3. Xen phu theo truc hu hieu hn xen phu theo
mat phang.

HC-A

V du

H 2:
1s

1s

HF:
2p

1s

F2 :
HC-A

2p

2p

V du
Xet phan t H2O :
Nguyen t trung tam O:

1s

2s

2p

Goc lien ket d


oan 90.

2p
1s

2s
HC-A

2p

Thc nghiem : 104 o

S tap chung orbital


Trc khi tao lien ket, cac orbital cua nguyen t se to
hp vi nhau tao ra cac orbital tap chung.
So orbital tap chung hnh thanh ung bang so orbital
tham gia to hp.

p
sp
sp

HC-A

Tap chung sp:BeF2

Be :
s

Kch thch:
Tap chung:
sp sp
HC-A

sp

sp

Tap chung sp

HC-A

Tap chung sp2 : BF3

B:
Kch thch:

sp2

Tap chung:
sp2 sp2 sp2
HC-A

sp2

sp2

Tap chung sp2

HC-A

Tap chung sp3 CH4

C:
Kch thch:

Tap chung:

sp3
sp3

sp3 sp3 sp3 sp3


HC-A

sp3

sp3

Tap chung sp3

HC-A

Tap chung sp3d va sp3d2

HC-A

Cac dang tap chung

HC-A

Cac dang tap chung

HC-A

V du
H H
Cong thc Lewis C2H4:H C = C H
Tam giac
p
H
sp2

H
HC-A

HC-A

C
sp2

sp2

Lien ket

H
Lien ket

- sp2

H C N

HCN:

Thang han- gsp

sp

V du

sp

p
Lien ket

bond
Lie
n ket

Lien ket Ba gom 1 va 2

HC-A

V du
CH2O:

H
sp2

C
sp2

sp2

Lien ket
HC-A

H C H
Tam giac

Lien ket

- sp2

HC-A

KHIEM KHUYET CUA THUYET


VB
S ton tai cua H2+
VB:

Khong the ton tai H2+ do moi lien ket ch c thc


hien bang 1 electron duy nhat

Thc te:

H2+ ton tai va kha ben vng


(nang lng lien ket trong H2+ la 255 kJ/mol)

HC-A

KHIEM KHUYET CUA THUYET


VB
Lien ket trong F2+ ben hn trong F2
VB:

lien ket cang ben khi mat o electron gia hai


nguyen t cang ln. Khi he F2 b mat i 1 electron
th mat o electron se giam i lam cho lien ket tr
nen kem ben hn.

Thc te:

lien ket trong F2+ (320 kJ/mol) ben hn lien ket


trong F2 (155 kJ/mol).

HC-A

KHIEM KHUYET CUA THUYET


VB
O2 thuan t (ton tai electron oc than trong
phan t O2)
VB:

Trong phan t O2 khong con electron oc than. Do


o O2 se co tnh nghch t (khong b nam cham hut. )

Thc te

O2 co tnh thuan t tc la b nam cham hut. ieu o


chng to rang trong phan t O2 van con co electron
oc than cha ghep cap.

HC-A

KHIEM KHUYET CUA THUYET


VB
Khong giai thch c hien tng
quang pho cua cac phan t cong hoa
tr.

HC-A

THUYET VAN AO PHAN T


MOLECULAR ORBITALS

m rong khai niem ham song cho


he phan t

HC-A

Luan iem
1. Trong phan t, cac electron cung ton tai
nhng trang thai rieng giong nh trong nguyen
t
2. Trang thai cua cac electron c bieu dien bi
cac ham song MO goi la cac orbital phan t.
3. Cac electron trong phan t cung chiem cac
orbital phan t tuan theo cac nguyen ly ben
vng, nguyen ly Pauli, quy tac Hund.
4. Viec xac nh cac ham song phan t (MO)
c thc hien bang cach giai phng trnh
song Schrodinger cho he phan t.
HC-A

Do tac dung tng ho gia cac hat


nhan va electron trong he phan t,
viec giai phng trnh Schrodinger la
rat phc tap.
e n gian hoa viec giai nay ta chap
nhan cac gia thuyet gan ung

HC-A

cac gia thuyet gan ung


1. Cac orbital phan t c hnh thanh t s to
hp tuyen tnh cua cac orbital nguyen t.
2. Cac orbital nguyen t tham gia to hp phai
thoa ieu kien:

Co nang lng gan nhau


Co tnh oi xng giong nhau

3. Ch co cac orbital hoa tr mi ong gop vao s


hnh thanh orbital phan t. Cac orbital nguyen
t lp vo ben trong khong b thay oi.
HC-A

cac gia thuyet gan ung


4. Tuy theo kieu to hp ma se tao thanh cac
orbital phan t co tnh oi xng va nang lng
khac nhau nh sau:

To hp oi xng qua truc se tao thanh cac orbital


phan t
To hp oi xng qua mat phang tao thanh cac
orbital phan t
To hp dng tao thanh cac orbital phan t co nang
lng thap goi la cac orbital lien ket (ky hieu la ,
hoac )
To hp am tao thanh cac orbital phan t co nang
lng cao goi la cac orbital phan lien ket (ky hieu la
* hoac * )

HC-A

Phan t H2
H2 cha orbital lien ket s1s va orbital phan lien
ket s*1s

HC-A

Phan t (X2) vi X la nguyen to chu ky 2


S to hp cua cac orbital nguyen t thanh cac
orbital phan t
1s + 1s 1s, 1s*
2s + 2s 2s, 2s*
(2px, 2py, 2pz) + (2px, 2py, 2pz)
2py, 2py*

2px, 2px*

2pz, 2pz*

Gia s truc Z trung vi truc lien ket


HC-A

Phan t O2
S hnh thanh 2pz MO:
2pz

2pz

2pz

HC-A

Phan t O2
S hnh thanh 2px MO:
2px

2px

HC-A

2px

Phan t O2
S hnh thanh *2px MO:
2px

HC-A

-2px

*2px

2p va 2p
*2pz
2pz
*2px
2px
*2py
HC-A

2py

S o orbital phan t
E

*2p
*2p
2p
2p
*2s
2s
*1s

HC-A

1s

2p

2s

1s

CACH SAP XEP ELECTRON


1. Tong so electron cua cac orbital phan t bang
tong so electron hoa tr ong gop bi cac
nguyen t
2. Cac electron sap xep vao cac orbital phan t
theo trat t nang lng t thap en cao
(nguyen ly ben vng)
3. Moi orbital phan t cha toi a 2 electron, hai
electron nay phai co spin ngc nhau (nguyen
ly loai tr Pauli)
4. Khi sap xep vao cac orbital co nang lng
bang nhau cac electron sap sao cho tong so
spin la cc ai (quy tac Hund)
HC-A

Bac lien ket


o ben cua lien ket trong phan t c xac nh
thong qua gia tr BAC LIEN KET
BAC LIEN KET = (Tong so electron tren
orbital lien ket Tong so electron tren
orbital phan lien ket)
Bac lien ket cang ln th lien ket trong phan t
cang ben.
Khi bac lien ket = 0 hay <0 th lien ket khong
ton tai.
HC-A

V du
He2: Bac LK = (2 - 2) = 0 phan t khong ton tai
*2p
*2p
E
2p
2p
*2s
2s
*1s
HC-A

1s

2p

2s

1s

V du
He2: Bac LK = (3 - 2) =
*2p
*2p
E
2p
2p
*2s
2s
*1s
1s

HC-A

2p

2s

1s

V du
N 2:
E

Bac LK = (10 - 4) = 3
*2p
*2p
2p
2p
*2s
2s
*1s

HC-A

1s

2p

2s

1s

S tng tac 2s - 2p
Khi nang lng cua orbital 2s va 2p cach xa
nhau (cac nguyen to cuoi chu ky nh O, F), s
tng tac gia 2s va 2p khong ang ke do o
cac orbital x , va y co nang lng cao hn
orbital 2p
Khi nang lng cua orbital 2s va 2p kha gan
nhau (cac nguyen to au chu ky nh B, C, N) ,
s tng tac gia 2s va 2p la ang ke do o cac
orbital x , va y co nang lng thap hn orbital
2p
HC-A

S tng tac 2s - 2p
Vi phan t O2 va F2 orbital s2p co nang lng
thap hn orbital p2p.

HC-A

V du
Phan t O2, F2, Ne2:
*2p
*2p

2p
2p
*2s
2s
*1s
1s

HC-A

2p

2s

1s

V du
O 2:

Bac LK = (10 - 6) = 2 thuan t


*2p
*2p
2p
2p
*2s
2s
*1s

HC-A

1s

2p

2s

1s

S ton tai cua H2+

HC-A

lien ket trong F2+ ben hn lien ket trong F2

HC-A

Bai tap ap dung

HC-A

Bai 1

Viet cong thc Lewis, d oan trang thai tap


chung cua nguyen t trung tam, xac nh hnh
dang phan t cua cac phan t sau:
CF4 , NF3 , OF2, BF3, BeH2 , TeF4 , AsF5 , KrF2
, KrF4 , SeF6 , XeOF4 , XeOF2 , XeO4

HC-A

Bai 2

D oan trang thai tap chung cua nguyen t


lu huynh trong cac phan t va ion sau:
SO2 ; SO3 ; SO42- ; S2O32- (co mach S-S-O) ;
S2O82- (co mach O-S-O-O-S-O) ; SF4; SF6 ;
SF2)

HC-A

Bai 3

Phan t allene co cong thc cau tao nh sau:


H2C=C=CH2 .Hay cho biet 4 nguyen t H co
nam tren cung mot mat phang hay khong?
Giai thch.

HC-A

Bai 4
Biacetyl (CH3(CO)2CH3) va acetoin
(CH3CH(OH)(CO)CH3) la hai hp chat c cho them
vao magarin lam cho magarin co mui v giong nh b.
Hay viet cong thc lewis, d oan trang thai tap
chung cua cac nguyen t cacbon trong hai phan t
nay.
Cho biet 4 nguyen t C va 2 nguyen t O trong
biacetyl co nam tren cung mot mat phang hay khong?
Giai thch.
O

HC-A

biacetyl

OH

acetoin

Bai 5

Trong so cac phan t va ion sau, phan t va


ion nao co the ton tai? Giai thch.
a) H2+ ; H2 ; H2- ; H22b) He2 ;He2+ ;He22+
C) Be2 ; Li2 ; B2

HC-A

Bai 6

Viet cau hnh electron theo thuyet MO cho cac


phan t va ion sau. Tnhtoan cac gia tr bac
lien ket. Cho biet chat nao la thuan t, nghch
t.
a) O2; O2+, O2-, O22b) CN, CN-; CN+
c) H2 ; B2 ; F2
d) N2 ; N2+ ; N2-

HC-A

Bai 7

Hay giai thch v sao nang lng ion hoa th


nhat cua phan t N2 (1501 KJ/mol) lai ln hn
nang lng ion hoa th nhat cua nguyen t N
(1402 KJ/mol)

HC-A

Bai 8

Phan t F2 co nang lng ion hoa th nhat ln


hn hay nho hn nang lng ion hoa th nhat
cua nguyen t F? Giai thch.

HC-A

Bai 9

S dung thuyet lien ket hoa tr va thuyet MO


e mo ta lien ket trong ion C22- (co trong phan
t CaC2)

HC-A

Bai 10

Mo ta lien ket trong NO; NO-; NO+ bang


thuyet lien ket hoa tr va thuyet MO. Da vao
thuyet MO hay d oan s bien oi ve o bien
lien ket, o dai noi N-O trong 3 phan t nay.

HC-A

Intermolecular Forces,
Liquids, and Solids
Lc lin kt lin phn t
Trng thi ngng kt ca vt cht

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Liquids and Solids: A Molecular Comparison

Tnh cht vt l ca cc cht c hiu theo khi


nim ca thuyt ng hc phn t (kinetic
molecular theory) nh sau:
Cht kh d b nn, c hnh dng v th tch ca
vt cha :
Cc phn t cht kh cch xa nhau, khng tng tc vi nhau.

Cht lng hu nh khng b nn, c hnh dng


(nhng khng c th tch) ca vt cha :
Cc phn t cht lng c gi gn nhau hn cc phn t
cht kh, nhng khng chc n mc chng khng th trt
qua nhau (slide past each other)

Cht rn khng b nn, c hnh dng v th tch


xc nh
Cc phn t cht rn c gi gn nhau. Cc phn t cht rn
c chc n mc chng khng th trt qua nhau c
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

A Molecular Comparison of Liquids and


Solids

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

A Molecular Comparison of Liquids and


Solids
Converting a gas into a liquid or solid requires
the molecules to get closer to each other/
bin i mt cht kh thnh lng hay rn:
cool or compress/ lm lnh hay nn

Converting a solid into a liquid or gas requires


the molecules to move further apart:/ bin i
mt cht rn thnh lng hay kh:
heat or reduce pressure/ gia nhit hay gim p sut

The forces holding solids and liquids together


are called intermolecular forces ( lc gi cc cht
lng v rn lai vi nhau c gi l lc lin phn t).
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Intermolecular Forces
The covalent bond holding a molecule together is
an intramolecular forces (lc ni phn t).
The attraction between molecules is an
intermolecular force (lc lin phn t)
Intermolecular forces are much weaker than
intramolecular forces (e.g. 16 kJ/mol vs. 431
kJ/mol for HCl).
When a substance melts (nng chy) or boils (si)
the intermolecular forces are broken (not the
covalent bonds).
When a substance condenses (ngng t)
intermolecular forces are formed.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Intermolecular Forces

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Intermolecular Forces
Ion-Dipole Forces (lc ion-lng cc)
Interaction between an ion (e.g. Na+) and a dipole
(e.g. water).
Strongest of all intermolecular forces:

QQ
F =k 1 2
d2

Since Q1 is a full charge and Q2 is a partial charge, F is


comparatively large.

F increases as Q increases and as d decreases:


the larger the charge and smaller the ion, the larger the
ion-dipole attraction.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Intermolecular Forces

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Intermolecular Forces
Dipole-Dipole Forces (lc lng cc-lng cc)
Interaction between a dipole (e.g. water) and a
dipole (e.g. water).
Dipole-dipole forces exist between neutral polar
molecules (gia cc phn t phn cc
trungho).
Polar molecules need to be close together.
Weaker than ion-dipole forces:

F =k

Q1Q2
d2

Q1 and Q2 are partial charges.


Copyright 1999, PRENTICE HALL

Chapter 9 and 10

Intermolecular Forces
Dipole--Dipole Forces
Dipole
There is a mix of attractive (ht)
and repulsive (y) dipoledipole forces as the molecules
tumble.
If two molecules have about the
same mass and size, then
dipole-dipole forces increase
with increasing polarity.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

10

Intermolecular Forces
London Dispersion Forces
Weakest of all intermolecular forces.
It is possible for two adjacent (k nhau) neutral
molecules to affect each other.
The nucleus of one molecule (or atom) attracts
the electrons of the adjacent molecule (or atom).
For an instant, the electron clouds become
distorted.
In that instant a dipole is formed (called an
instantaneous dipole-lng cc tm thi).
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

11

Intermolecular Forces
London Dispersion Forces

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

12

Intermolecular Forces
London Dispersion Forces
One instantaneous dipole can induce (tc ng)
another instantaneous dipole in an adjacent
molecule (or atom).
The forces between instantaneous dipoles are
called London dispersion forces.
Polarizability is the ease with which an electron
cloud can be deformed.
The larger the molecule (the greater the number
of electrons) the more polarizable.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

13

Intermolecular Forces
London Dispersion Forces

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

14

Intermolecular Forces
London Dispersion Forces
London dispersion forces increase as molecular
weight increases.
London dispersion forces exist between all
molecules.
London dispersion forces depend on the shape
of the molecule.
The greater the surface area available for
contact, the greater the dispersion forces.
London dispersion forces between spherical
(dng cu) molecules are lower than between
sausage-like (dng xc xch) molecules.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

15

Intermolecular Forces

Hydrogen Bonding (lin kt Hydro)


Special case of dipole-dipole forces.
By experiments: boiling points of compounds
with H-F, H-O, and H-N bonds are abnormally
high.
Intermolecular forces are abnormally strong.
H-bonding requires H bonded to an
electronegative element (most important for
compounds of F, O, and N).
Electrons in the H-X (X = electronegative element) lie
much closer to X than H.
H has only one electron, so in the H-X bond, the + H
presents an almost bare proton to the - X.
Copyright
1999, PRENTICE HALL
Chapter
9 and 10
16
Therefore,
H-bonds are
strong.

Intermolecular Forces
Hydrogen Bonding

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

17

Intermolecular Forces
Hydrogen Bonding
Hydrogen bonds are responsible for:
Ice Floating
Solids are usually more closely packed than liquids;
therefore, solids are more dense than liquids.
Ice is ordered with an open structure to optimize Hbonding.
Therefore, ice is less dense than water.
In water the H-O bond length is 1.0 .
The OH hydrogen bond length is 1.8 .
Ice has waters arranged in an open, regular hexagon.
Each + H points towards a lone pair on O.
Ice floats, so it forms an insulating layer on top of lakes,
rivers,
etc. Therefore,
aquatic
life can survive in winter.
Copyright
1999, PRENTICE
HALL
Chapter 9 and 10
18

Intermolecular Forces
Hydrogen Bonding
Hydrogen bonds are responsible for:
Protein Structure
Protein folding is a consequence of H-bonding.
DNA Transport of Genetic Information

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

19

Intermolecular Forces
Comparing Intermolecular Forces

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

20

Some Properties of Liquids


Viscosity ( nht)
Viscosity is the resistance of a liquid to flow.
A liquid flows by sliding molecules over each
other.
The stronger the intermolecular forces, the
higher the viscosity.

Surface Tension (sc cng b mt)


Bulk molecules (those in the liquid) are equally
attracted to their neighbors.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

21

Some Properties of Liquids


Surface Tension

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

22

Some Properties of Liquids


Surface Tension
Surface molecules are only attracted inwards
towards the bulk molecules.
Therefore, surface molecules are packed more
closely than bulk molecules.

Surface tension is the amount of energy


required to increase the surface area of a liquid.
Cohesive forces (lc c kt) bind molecules to
each other.
Adhesive forces (lc kt dnh) bind molecules to
a surface.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

23

Some Properties of Liquids


Surface Tension

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

24

Some Properties of Liquids


Surface Tension
Meniscus is the shape of the liquid surface.
If adhesive forces are greater than cohesive forces,
the liquid surface is attracted to its container more
than the bulk molecules. Therefore, the meniscus is
U-shaped (e.g. water in glass).
If cohesive forces are greater than adhesive forces,
the meniscus is curved downwards.

Capillary Action: When a narrow glass tube is


placed in water, the meniscus pulls the water up
the tube.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

25

Phase Changes
Surface molecules are only attracted inwards
towards the bulk molecules.
Sublimation: solid gas.
Vaporization: liquid gas.
Melting or fusion: solid liquid.
Deposition: gas solid.
Condensation: gas liquid.
Freezing: liquid solid.

Energy Changes Accompanying Phase


Changes
Energy change of the system for the above
processes
are:
Copyright
1999, PRENTICE HALL
Chapter 9 and 10

26

Phase Changes
Energy Changes Accompanying Phase
Changes

Sublimation: Hsub > 0 (endothermic).


Vaporization: Hvap > 0 (endothermic).
Melting or Fusion: Hfus > 0 (endothermic).
Deposition: Hdep < 0 (exothermic).
Condensation: Hcon < 0 (exothermic).
Freezing: Hfre < 0 (exothermic).

Generally heat of fusion (enthalpy of fusion) is


less than heat of vaporization:
it takes more energy to completely separate
molecules, than partially separate them.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

27

Phase Changes
Energy Changes Accompanying Phase
Changes
All phase changes are possible under the right
conditions (e.g. water sublimes when snow
disappears without forming puddles).
The sequence
heat solid melt heat liquid boil heat gas
is endothermic.
The sequence
cool gas condense cool liquid freeze
cool solid
is exothermic.
Copyright 1999, PRENTICE HALL
Chapter 9 and 10
28

Phase Changes
Energy Changes Accompanying Phase Changes

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

29

Phase Changes
Heating Curves / Cooling curves
Plot of temperature change versus heat added is
a heating curve.
During a phase change, adding heat causes no
temperature change.
These points are used to calculate Hfus and Hvap.

Supercooling: When a liquid is cooled below its


melting point and it still remains a liquid.
Achieved by keeping the temperature low and
increasing kinetic energy to break
intermolecular forces.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

30

Phase Changes
Heating Curves

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

31

Phase Changes
Critical Temperature and Pressure
Gases liquefied by increasing pressure at some
temperature.
Critical temperature (nhit ti hn) : the
minimum temperature for liquefaction of a gas
using pressure.
Critical pressure (p sut ti hn): pressure
required for liquefaction.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

32

Vapor Pressure
Explaining Vapor Pressure on the Molecular
Level
Some of the molecules on the surface of a liquid have
enough energy to escape the attraction of the bulk
liquid.
These molecules move into the gas phase.
As the number of molecules in the gas phase
increases, some of the gas phase molecules strike the
surface and return to the liquid.
After some time the pressure of the gas will be
constant at the vapor pressure.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

33

Vapor Pressure
Explaining Vapor Pressure on
the Molecular Level
Dynamic Equilibrium: the
point when as many molecules
escape the surface as strike the
surface.
Vapor pressure is the pressure
exerted when the liquid and
vapor are in dynamic
equilibrium.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

34

Vapor Pressure
Volatility, Vapor Pressure, and Temperature
If equilibrium is never established then the liquid
evaporates.
Volatile substances evaporate rapidly.
The higher the temperature, the higher the average
kinetic energy, the faster the liquid evaporates.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

35

Vapor Pressure
Volatility, Vapor Pressure, and Temperature

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

36

Vapor Pressure
Vapor Pressure and Boiling Point
Liquids boil when the external pressure equals the
vapor pressure.
Temperature of boiling point increases as pressure
increases.
Two ways to get a liquid to boil: increase temperature
or decrease pressure.
Pressure cookers operate at high pressure. At high pressure
the boiling point of water is higher than at 1 atm.
Therefore, there is a higher temperature at which the food is
cooked, reducing the cooking time required.

Normal boiling point is the boiling point at 760 mmHg


(1 atm).
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

37

Phase Diagrams
Phase diagram: plot of pressure vs. Temperature
summarizing all equilibria between phases.
Given a temperature and pressure, phase diagrams
tell us which phase will exist.
Features of a phase diagram:
Triple point: temperature and pressure at which all three
phases are in equilibrium.
Vapor-pressure curve: generally as pressure increases,
temperature increases.
Critical point: critical temperature and pressure for the gas.
Melting point curve: as pressure increases, the solid phase is
favored if the solid is more dense than the liquid.
Normal melting point: melting point at 1 atm.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

38

Phase Diagrams
Any temperature and pressure combination not on a
curve represents a single phase.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

39

Phase Diagrams
The Phase Diagrams of H2O and CO2
Water:
The melting point curve slopes to the left because ice is less
dense than water.
Triple point occurs at 0.0098C and 4.58 mmHg.
Normal melting (freezing) point is 0C.
Normal boiling point is 100C.
Critical point is 374C and 218 atm.

Carbon Dioxide:
Triple point occurs at -56.4C and 5.11 atm.
Normal sublimation point is -78.5C. (At 1 atm CO2
sublimes it does not melt.)
Critical point occurs at 31.1C and 73 atm.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

40

Phase Diagrams
The Phase Diagrams of H2O and CO2

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

41

Structures of Solids
Unit Cells
Crystalline solid: well-ordered, definite arrangements
of molecules, atoms or ions.
Crystals have an ordered, repeated structure.
The smallest repeating unit in a crystal is a unit cell.
Unit cell is the smallest unit with all the symmetry of
the entire crystal.
Three-dimensional stacking of unit cells is the crystal
lattice.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

42

Structures of Solids
Unit Cells

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

43

Structures of Solids
Unit Cells
Three common types of unit cell.
Primitive cubic, atoms at the corners of a simple cube,
each atom shared by 8 unit cells;

Body-centered cubic (bcc), atoms at the corners of a cube


plus one in the center of the body of the cube,
corner atoms shared by 8 unit cells, center atom completely enclosed in
one unit cell;

Face-centered cubic (fcc), atoms at the corners of a cube


plus one atom in the center of each face of the cube,
corner atoms shared by 8 unit cells, face atoms shared by 2 unit
cells.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

44

Structures of Solids
Unit Cells

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

45

Structures of Solids
Crystal Structure of Sodium Chloride
Face-centered cubic lattice.
Two equivalent ways of defining unit cell:
Cl- (larger) ions at the corners of the cell, or
Na+ (smaller) ions at the corners of the cell.

The cation to anion ratio in a unit cell is the same for


the crystal. In NaCl each unit cell contains same
number of Na+ and Cl- ions.
Note the unit cell for CaCl2 needs twice as many Clions as Ca2+ ions.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

46

Structures of Solids
Crystal Structure of Sodium Chloride

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

47

Structures of Solids
Close Packing of Spheres
Solids have maximum intermolecular forces.
Molecules can be modeled by spheres.
Atoms and ions are spheres.
Molecular crystals are formed by close packing of the
molecules.
We rationalize maximum intermolecular force in a
crystal by the close packing of spheres.
When spheres are packed as closely as possible, there
are small spaces between adjacent spheres.
The spaces are called interstitial holes.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

48

Structures of Solids
Close Packing of Spheres

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

49

Structures of Solids
Close Packing of Spheres
A crystal is built up by placing close packed layers of
spheres on top of each other.
There is only one place for the second layer of spheres.
There are two choices for the third layer of spheres:
Third layer eclipses the first (ABAB arrangement). This is
called hexagonal close packing (hcp);
Third layer is in a different position relative to the first
(ABCABC arrangement). This is called cubic close packing
(ccp).

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

50

Structures of Solids
Close Packing of Spheres

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Chapter 9 and 10

51

Structures of Solids
Close Packing of Spheres
Each sphere is surrounded by 12 other spheres (6 in
one plane, 3 above and 3 below).
Coordination number: the number of spheres directly
surrounding a central sphere.
Hexagonal and cubic close packing are different from
the cubic unit cells.
If unequally sized spheres are used, the smaller
spheres are placed in the interstitial holes.

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

52

Structures of Solids
X-Ray Diffraction
When waves are passed through a narrow slit
they are diffracted.
When waves are passed through a diffraction
grating (many narrow slits in parallel) they
interact to form a diffraction pattern (areas of
light and dark bands).
Efficient diffraction occurs when the wavelength
of light is close to the size of the slits.
The spacing between layers in a crystal is 2 - 20
, which is the wavelength range for X-rays.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

53

Structures of Solids
X-Ray Diffraction

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

54

Structures of Solids
X-Ray Diffraction
X-ray diffraction (X-ray crystallography):
X-rays are passed through the crystal and are
detected on a photographic plate.
The photographic plate has one bright spot at the
center (incident beam) as well as a diffraction pattern.
Each close packing arrangement produces a different
diffraction pattern.
Knowing the diffraction pattern, we can calculate the
positions of the atoms required to produce that
pattern.
We calculate the crystal structure based on a
knowledge of the diffraction pattern.
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

55

Bonding in Solids
There are four types of solid:
Molecular (formed from molecules) - usually
soft with low melting points and poor
conductivity.
Covalent network (formed from atoms) - very
hard with very high melting points and poor
conductivity.
Ions (formed form ions) - hard, brittle, high
melting points and poor conductivity.
Metallic (formed from metal atoms) - soft or
hard, high melting points, good conductivity,
malleable and ductile.
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Chapter 9 and 10

56

Bonding in Solids

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

57

Bonding in Solids
Molecular Solids
Intermolecular forces: dipole-dipole, London
dispersion and H-bonds.
Weak intermolecular forces give rise to low
melting points.
Room temperature gases and liquids usually
form molecular solids at low temperature.
Efficient packing of molecules is important
(since they are not regular spheres).

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

58

Bonding in Solids
Covalent Network Solids
Intermolecular forces: dipole-dipole, London
dispersion and H-bonds.
Atoms held together in large networks.
Examples: diamond, graphite, quartz (SiO2),
silicon carbide (SiC), and boron nitride (BN).
In diamond:

each C atom has a coordination number of 4;


each C atom is tetrahedral;
there is a three-dimensional array of atoms.
Diamond is hard, and has a high melting point (3550
C).

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

59

Bonding in Solids
Covalent Network Solids

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Chapter 9 and 10

60

Bonding in Solids
Covalent Network Solids
In graphite
each C atom is arranged in a planar hexagonal ring;
layers of interconnected rings are placed on top of
each other;
the distance between C atoms is close to benzene
(1.42 vs. 1.395 in benzene);
the distance between layers is large (3.41 );
electrons move in delocalized orbitals (good
conductor).

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

61

Bonding in Solids
Ionic Solids
Ions (spherical) held together by electrostatic
forces of attraction:

F =k

Q1Q2
d2

The higher the charge (Q) and smaller the distance (d)
between ions, the stronger the ionic bond.

There are some simple classifications for ionic


lattice types:

Copyright 1999, PRENTICE HALL

Chapter 9 and 10

62

Bonding in Solids
Ionic Solids

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Chapter 9 and 10

63

Bonding in Solids
Ionic Solids
NaCl Structure
Each ion has a coordination number of 6.
Face-centered cubic lattice.
Cation to anion ratio is 1:1.
Examples: LiF, KCl, AgCl and CaO.
CsCl Structure
Cs+ has a coordination number of 8.
Different from the NaCl structure (Cs+ is larger than
Na+).
Cation to anion ratio is 1:1.

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Chapter 9 and 10

64

Bonding in Solids

Ionic Solids
Zinc Blende Structure
Typical example ZnS.
S2- ions adopt a fcc arrangement.
Zn2+ ions have a coordination number of 4.
The S2- ions are placed in a tetrahedron around the
Zn2+ ions.
Example: CuCl.
Fluorite Structure
Typical example CaF2.
Ca2+ ions in a fcc arrangement.
There are twice as many F- per Ca2+ ions in each unit
cell.
Examples: BaCl2, PbF2.

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Chapter 9 and 10

65

Bonding in Solids
Metallic Solids
Metallic solids have metal atoms in hcp, fcc or
bcc arrangements.
Coordination number for each atom is either 8
or 12.
Problem: the bonding is too strong for London
dispersion and there are not enough electrons
for covalent bonds.
Resolution: the metal nuclei float in a sea of
electrons.
Metals conduct because the electrons are
delocalized and are mobile.
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Chapter 9 and 10

66

Bonding in Solids
Metallic Solids

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Chapter 9 and 10

67

Intermolecular Forces,
Liquids, and Solids

End of Chapter 11
Copyright 1999, PRENTICE HALL

Chapter 9 and 10

68

Properties of Solutions
David P. White
University of North Carolina, Wilmington

Chapter 13
Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


A solution is a homogeneous mixture of solute
(present in smallest amount) and solvent (present in
largest amount).
Solutes and solvent are components of the solution.
In the process of making solutions with condensed
phases, intermolecular forces become rearranged.
Consider NaCl (solute) dissolving in water (solvent):

the water H-bonds have to be interrupted,


NaCl dissociates into Na+ and Cl-,
ion-dipole forces form: Na+ -OH2 and Cl- +H2O.
We say the ions are solvated by water.
If water is the solvent, we say the ions are hydrated.

Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process

Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Energy Changes and Solution Formation
There are three energy steps in forming a solution:
separation of solute molecules (
H1),
separation of solvent molecules (
H2), and
formation of solute-solvent interactions (
H3).

We define the enthalpy change in the solution process


as
Hsoln = H1 + H2 + H3.
Hsoln can either be positive or negative depending on
the intermolecular forces.

Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Energy Changes and Solution Formation

Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Energy Changes and Solution Formation
Breaking attractive intermolecular forces is always
endothermic.
Forming attractive intermolecular forces is always
exothermic.
To determine whether Hsoln is positive or negative,
we consider the strengths of all solute-solute and
solute-solvent interactions:
H1 and H2 are both positive.
H3 is always negative.
It is possible to have either H3 > (
H1 + H2) or H3 <
(
H1 + H2).
Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Energy Changes and Solution Formation

Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Energy Changes and Solution Formation
Examples:
NaOH added to water has Hsoln = -44.48 kJ/mol.
NH4NO3 added to water has Hsoln = + 26.4 kJ/mol.

Rule: polar solvents dissolve polar solutes. Nonpolar solvents dissolve non-polar solutes. Why?
If Hsoln is too endothermic a solution will not form.
NaCl in gasoline: the ion-dipole forces are weak because
gasoline is non-polar. Therefore, the ion-dipole forces do
not compensate for the separation of ions.
Water in octane: water has strong H-bonds. There are no
attractive forces between water and octane to compensate
for the H-bonds.
Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Solution Formation, Spontaneity, and Disorder
A spontaneous process occurs without outside
intervention.
When energy of the system decreases (e.g. dropping a
book and allowing it to fall to a lower potential
energy), the process is spontaneous.
Some spontaneous processes do not involve the system
moving to a lower energy state (e.g. an endothermic
reaction).
If the process leads to a greater state of disorder, then
the process is spontaneous.
Copyright 1999, PRENTICE HALL

Chapter 13

The Solution Process


Solution Formation, Spontaneity, and Disorder
Example: a mixture of CCl4 and C6H14 is less ordered
than the two separate liquids. Therefore, they
spontaneously mix even though Hsoln is very close to
zero.
There are solutions that form by physical processes
and those by chemical processes.

Copyright 1999, PRENTICE HALL

Chapter 13

10

The Solution Process


Solution Formation, Spontaneity, and Disorder

Copyright 1999, PRENTICE HALL

Chapter 13

11

The Solution Process


Solution Formation and Chemical Reactions
Example: a mixture of CCl4 and C6H14 is less ordered
Consider:
Ni(s) + 2HCl(aq) NiCl2(aq) + H2(g).
Note the chemical form of the substance being
dissolved has changed (Ni NiCl2).
When all the water is removed from the solution, no
Ni is found only NiCl2.6H2O. Therefore, Ni
dissolution in HCl is a chemical process.

Copyright 1999, PRENTICE HALL

Chapter 13

12

The Solution Process


Solution Formation and Chemical Reactions

Copyright 1999, PRENTICE HALL

Chapter 13

13

The Solution Process


Solution Formation and Chemical Reactions
Example:
NaCl(s) + H2O (l) Na+(aq) + Cl-(aq).
When the water is removed from the solution, NaCl is
found. Therefore, NaCl dissolution is a physical
process.

Copyright 1999, PRENTICE HALL

Chapter 13

14

Ways of Expressing Concentration


All methods involve quantifying amount of solute per
amount of solvent (or solution).
Generally amounts or measures are masses, moles or
liters.
Qualitatively solutions are dilute or concentrated.
Definitions:
mass of component in soln
Mass % of component =
100
total mass of soln
ppm of component =

Copyright 1999, PRENTICE HALL

mass of component in soln


106
total mass of soln
Chapter 13

15

Ways of Expressing Concentration


Parts per million (ppm) can be expressed as 1 mg of
solute per kilogram of solution.
If the density of the solution is 1g/mL, then 1 ppm = 1 mg
solute per liter of solution.

Parts per billion (ppb) are 1 g of solute per kilogram


of solution.

Copyright 1999, PRENTICE HALL

Chapter 13

16

Ways of Expressing Concentration


Mole Fraction, Molarity, and Molality
Recall mass can be converted to moles using the
molar mass.
Recall
moles of component
Mole fraction of component =
total moles of all components
Recall
Molarity =

Copyright 1999, PRENTICE HALL

moles of solute
liters of solution

Chapter 13

17

Ways of Expressing Concentration


Mole Fraction, Molarity, and Molality
We define

Molality =

moles of solute
kilograms of solution

Converting between molarity (M) and molality (m)


requires density.

Copyright 1999, PRENTICE HALL

Chapter 13

18

Ways of Expressing Concentration


Mole Fraction, Molarity, and Molality

Copyright 1999, PRENTICE HALL

Chapter 13

19

Saturated Solutions and Solubility


Mole Fraction, Molarity, and Molality
Dissolve: solute + solvent solution.
Crystallization: solution solute + solvent.
Saturation: crystallization and dissolution are in
equilibrium.
Solubility: amount of solute required to form a
saturated solution.
Supersaturated: a solution formed when more solute
is dissolved than in a saturated solution.

Copyright 1999, PRENTICE HALL

Chapter 13

20

Factors Affecting Solubility


Solute--Solvent Interactions
Solute
Polar liquids tend to dissolve in polar solvents.
Miscible liquids: mix in any proportions.
Immiscible liquids: do not mix.
Intermolecular forces are important: water and
ethanol are miscible because the broken hydrogen
bonds in both pure liquids are re-established in the
mixture.
The number of carbon atoms in a chain affect
solubility: the more C atoms the less soluble in water.

Copyright 1999, PRENTICE HALL

Chapter 13

21

Factors Affecting Solubility


Solute--Solvent Interactions
Solute

Copyright 1999, PRENTICE HALL

Chapter 13

22

Factors Affecting Solubility


Solute--Solvent Interactions
Solute
The number of -OH groups within a molecule
increases solubility in water.

Copyright 1999, PRENTICE HALL

Chapter 13

23

Factors Affecting Solubility


Solute--Solvent Interactions
Solute
Generalization: like dissolves like.
The more polar bonds in the molecule, the better it
dissolves in a polar solvent.
The less polar the molecule the less it dissolves in a
polar solvent and the better is dissolves in a non-polar
solvent.
Network solids do not dissolve because the strong
intermolecular forces in the solid are not reestablished in any solution.

Copyright 1999, PRENTICE HALL

Chapter 13

24

Factors Affecting Solubility


Pressure Effects
Solubility of a gas in a liquid is a function of the
pressure of the gas.
The higher the pressure, the more molecules of gas
are close to the solvent and the greater the chance of a
gas molecule striking the surface and entering the
solution.
Therefore, the higher the pressure, the greater the solubility.
The lower the pressure, the fewer molecules of gas are close
to the solvent and the lower the solubility.

Copyright 1999, PRENTICE HALL

Chapter 13

25

Factors Affecting Solubility


Pressure Effects

Copyright 1999, PRENTICE HALL

Chapter 13

26

Factors Affecting Solubility


Pressure Effects
Henrys Law:

C g = kPg
Cg is the solubility of gas, Pg the partial pressure, k =
Henrys law constant.
Carbonated beverages are bottled under PCO2 > 1 atm.
As the bottle is opened, PCO2 decreases and the
solubility of CO2 decreases. Therefore, bubbles of
CO2 escape from solution.
Copyright 1999, PRENTICE HALL

Chapter 13

27

Factors Affecting Solubility


Temperature Effects
Experience tells us that sugar dissolves better in warm
water than cold.
As temperature increases, solubility of solids generally
increases.
Sometimes, solubility decreases as temperature
increases (e.g. Ce2(SO4)3).

Copyright 1999, PRENTICE HALL

Chapter 13

28

Factors Affecting Solubility


Temperature Effects

Copyright 1999, PRENTICE HALL

Chapter 13

29

Factors Affecting Solubility


Temperature Effects

Experience tells us that carbonated beverages go flat as


they get warm.

Copyright 1999, PRENTICE HALL

Chapter 13

30

Factors Affecting Solubility


Temperature Effects
Experience tells us that carbonated beverages go flat
as they get warm.
Gases are less soluble at higher temperatures.
Thermal pollution: if lakes get too warm, CO2 and O2
become less soluble and are not available for plants or
animals.

Copyright 1999, PRENTICE HALL

Chapter 13

31

Colligative Properties
Colligative properties depend on quantity of solute
molecules. (E.g. freezing point depression and
melting point elevation.)

Lowering the Vapor Pressure


Non-volatile solvents reduce the ability of the surface
solvent molecules to escape the liquid.
Therefore, vapor pressure is lowered.
The amount of vapor pressure lowering depends on
the amount of solute.
Copyright 1999, PRENTICE HALL

Chapter 13

32

Colligative Properties
Lowering the Vapor Pressure

Copyright 1999, PRENTICE HALL

Chapter 13

33

Colligative Properties
Raoults Law
Raoults Law: PA is the vapor pressure with solute,
PA is the vapor pressure without solvent, and A is
the mole fraction of A, then

PA = A PA
Recall Daltons Law:

PA = A Ptotal

Copyright 1999, PRENTICE HALL

Chapter 13

34

Colligative Properties
Raoults Law
Ideal solution: one that obeys Raoults law.
Raoults law breaks down when the solvent-solvent
and solute-solute intermolecular forces are greater
than solute-solvent intermolecular forces.

Boiling--Point Elevation
Boiling
Goal: interpret the phase diagram for a solution.
Non-volatile solute lowers the vapor pressure.
Therefore the triple point - critical point curve is
lowered.
Copyright 1999, PRENTICE HALL

Chapter 13

35

Colligative Properties
Boiling--Point Elevation
Boiling

Copyright 1999, PRENTICE HALL

Chapter 13

36

Colligative Properties
Boiling--Point Elevation
Boiling
At 1 atm (normal boiling point of pure liquid) there is
a lower vapor pressure of the solution. Therefore, a
higher temperature is required to teach a vapor
pressure of 1 atm for the solution (
Tb).
Molal boiling-point-elevation constant, Kb, expresses
how much Tb changes with molality, m:

Tb = K b m

Copyright 1999, PRENTICE HALL

Chapter 13

37

Colligative Properties
Freezing--Point Depression
Freezing
At 1 atm (normal boiling point of pure liquid) there is
no depression by definition
When a solution freezes, almost pure solvent is
formed first.
Therefore, the sublimation curve for the pure solvent is the
same as for the solution.
Therefore, the triple point occurs at a lower temperature
because of the lower vapor pressure for the solution.

The melting-point (freezing-point) curve is a vertical


line from the triple point.
Copyright 1999, PRENTICE HALL

Chapter 13

38

Colligative Properties
Freezing--Point Depression
Freezing
The solution freezes at a lower temperature (
Tf) than
the pure solvent.
Decrease in freezing point (
Tf) is directly
proportional to molality (Kf is the molal freezingpoint-depression constant):

T f = K f m

Copyright 1999, PRENTICE HALL

Chapter 13

39

Colligative Properties
Freezing--Point Depression
Freezing

Copyright 1999, PRENTICE HALL

Chapter 13

40

Colligative Properties
Osmosis
Semipermeable membrane: permits passage of some
components of a solution. Example: cell membranes
and cellophane.
Osmosis: the movement of a solvent from low solute
concentration to high solute concentration.
There is movement in both directions across a
semipermeable membrane.
As solvent moves across the membrane, the fluid
levels in the arms becomes uneven.

Copyright 1999, PRENTICE HALL

Chapter 13

41

Colligative Properties
Osmosis
Eventually the pressure difference between the arms
stops osmosis.

Copyright 1999, PRENTICE HALL

Chapter 13

42

Colligative Properties
Osmosis
Osmotic pressure, , is the pressure required to stop
osmosis:

V = nRT
n
= RT
V
= MRT

Copyright 1999, PRENTICE HALL

Chapter 13

43

Colligative Properties
Osmosis
Osmotic pressure, , is the pressure required to stop
osmosis:
Isotonic solutions: two solutions with the same
separated by a semipermeable membrane.
Hypotonic solutions: a solution of lower than a
hypertonic solution.
Osmosis is spontaneous.
Red blood cells are surrounded by semipermeable
membranes.
Copyright 1999, PRENTICE HALL

Chapter 13

44

Colligative Properties
Osmosis
Crenation:
red blood cells placed in hypertonic solution (relative to
intracellular solution);
there is a lower solute concentration in the cell than the
surrounding tissue;
osmosis occurs and water passes through the membrane out
of the cell.
The cell shrivels up.

Copyright 1999, PRENTICE HALL

Chapter 13

45

Colligative Properties
Osmosis
Crenation and Hemolysis:

Copyright 1999, PRENTICE HALL

Chapter 13

46

Colligative Properties
Osmosis
Hemolysis:

red blood cells placed in a hypotonic solution;


there is a higher solute concentration in the cell;
osmosis occurs and water moves into the cell.
The cell bursts.

To prevent crenation or hemolysis, IV (intravenous)


solutions must be isotonic.
Examples of osmosis:
Cucumber placed in NaCl solution loses water to shrivel up
and become a pickle.
Copyright 1999, PRENTICE HALL

Chapter 13

47

Colligative Properties
Osmosis
Limp carrot placed in water becomes firm because water
enters via osmosis.
Salty food causes retention of water and swelling of tissues
(edema).
Water moves into plants through osmosis.
Salt added to meat or sugar to fruit prevents bacterial
infection (a bacterium placed on the salt will lose water
through osmosis and die).

Active transport is the movement of nutrients and


waste material through a biological system.
Active transport is not spontaneous.
Copyright 1999, PRENTICE HALL

Chapter 13

48

Colloids
Colloids are suspensions in which the suspended
particles are larger than molecules but too small to
drop out of the suspension due to gravity.
Particle size: 10 to 2000 .
There are several types of colloid:

aerosol (gas + liquid or solid, e.g. fog and smoke),


foam (liquid + gas, e.g. whipped cream),
emulsion (liquid + liquid, e.g. milk),
sol (liquid + solid, e.g. paint),
solid foam (solid + gas, e.g. marshmallow),
solid emulsion (solid + liquid, e.g. butter),
solid sol (solid + solid, e.g. ruby glass).

Copyright 1999, PRENTICE HALL

Chapter 13

49

Colloids
Tyndall effect: ability of a Colloid to scatter light. The
beam of light can be seen through the colloid.

Copyright 1999, PRENTICE HALL

Chapter 13

50

Colloids
Hydrophilic and Hydrophobic Colloids
Focus on colloids in water.
Water loving colloids: hydrophilic.
Water hating colloids: hydrophobic.
Molecules arrange themselves so that hydrophobic
portions are oriented towards each other.
If a large hydrophobic macromolecule (giant
molecule) needs to exist in water (e.g. in a cell),
hydrophobic molecules embed themselves into the
macromolecule leaving the hydrophilic ends to
interact with water.

Copyright 1999, PRENTICE HALL

Chapter 13

51

Colloids
Hydrophilic and Hydrophobic Colloids

Copyright 1999, PRENTICE HALL

Chapter 13

52

Colloids
Hydrophilic and Hydrophobic Colloids
Typical hydrophilic groups are polar (containing C-O,
O-H, N-H bonds) or charged.
Hydrophobic colloids need to be stabilized in water.
Adsorption: when something sticks to a surface we
say that it is adsorbed.
If ions are adsorbed onto the surface of a colloid, the
colloids appears hydrophilic and is stabilized in water.
Consider a small drop of oil in water.
Add to the water sodium stearate.
Copyright 1999, PRENTICE HALL

Chapter 13

53

Colloids
Hydrophilic and Hydrophobic Colloids

Copyright 1999, PRENTICE HALL

Chapter 13

54

Colloids
Hydrophilic and Hydrophobic Colloids
Sodium stearate has a long hydrophobic tail
(CH3(CH2)16-) and a small hydrophobic head (-CO2Na+).
The hydrophobic tail can be absorbed into the oil
drop, leaving the hydrophilic head on the surface.
The hydrophilic heads then interact with the water
and the oil drop is stabilized in water.

Copyright 1999, PRENTICE HALL

Chapter 13

55

Colloids
Hydrophilic and Hydrophobic Colloids

Copyright 1999, PRENTICE HALL

Chapter 13

56

Colloids
Hydrophilic and Hydrophobic Colloids
Most dirt stains on people and clothing are oil-based.
Soaps are molecules with long hydrophobic tails and
hydrophilic heads that remove dirt by stabilizing the
colloid in water.
Bile excretes substances like sodium stereate that
forms an emulsion with fats in our small intestine.
Emulsifying agents help form an emulsion.

Copyright 1999, PRENTICE HALL

Chapter 13

57

Colloids
Removal of Colloidal Particles
Colloid particles are too small to be separated by
physical means (e.g. filtration).
Colloid particles are coagulated (enlarged) until they
can be removed by filtration.
Methods of coagulation:
heating (colloid particles move and are attracted to each
other when they collide);
adding an electrolyte (neutralize the surface charges on the
colloid particles).

Dialysis: using a semipermeable membranes separate


ions from colloidal particles.
Copyright 1999, PRENTICE HALL

Chapter 13

58

Properties of Solutions

End of Chapter 13
Copyright 1999, PRENTICE HALL

Chapter 13

59

NHIET ONG HOA HOC

CHEMICAL THERMODYNAMICS

MUC TIEU CUA NHIET ONG HOC


Nghien cu cac quy luat ve s bien chuyen tng
ho cua hoa nang va cac dang nang lng khac
trong cac qua trnh hoa hoc.
Nghien cu cac ieu kien t dien bien
(phan ng hoa hoc) va cac ieu kien ben vng
(trang thai can bang) cua cac he hoa hoc.

MOT SO KHAI NIEM C BAN


Systems and Surroundings (H
thng v mi trng)
System (H thng): part of the
universe we are interested in.
Surroundings(mi trng ): the
rest of the universe.

MOT SO KHAI NIEM C BAN


He hoa hoc la lng nhat nh cua mot hay nhieu
chat ieu kien nhiet o, ap suat va nong o nhat
nh(trong nghin cu nhit ng hc goi la he
thng - system)
H m l h trao i c vt cht v nng lng vi mi
trng
H kn l h ch trao i nng lng vi mi trng
He co lap la he khong co s trao oi nng lng va
vt chat vi moi trng ben ngoai.
4

MOT SO KHAI NIEM C BAN


He ong the la he co cac tnh chat hoa hoc va vat
ly giong nhau trong toan bo the tch cua he.
He d the la he co be mat phan chia cac phan cua
he thanh nhng phan co tnh chat hoa hoc va vat
ly khac nhau.
Pha la phan ong the cua he d the co thanh phan ,
cau tao , tnh chat nhat nh va c phan chia
vi cac phan khac bang be mat phan chia nao
o.
5

MOT SO KHAI NIEM C BAN


Nhiet dung (C) cua mot chat la lng nhiet can dung e nang nhiet o
cua mot lng xac nh chat o len mot o.
Nhiet dung rieng la lng nhiet can dung e nang mot gam chat o
len mot o.
Nhiet dung phan t la lng nhiet can dung e nang mot mol chat o
len mot o.
Nhiet dung ang ap la nhiet dung cua qua trnh nang nhiet trong ieu
kien ang ap, ky hieu CP .
Nhiet dung ang tch la nhiet dung cua qua trnh nang nhiet trong ieu
kien ang tch, Ky hieu CV. oi vi kh ly tng, xet cho 1 mol kh
th: Cp=5R/2 ; Cv =3R/2; vi R=8,3145 J/mol. o
V du : Nhiet dung rieng ang ap cua nc trong khoang 14,50C
15,50C bang 1 cal / g.o , nhiet dung phan t ang ap cua nc
trong khoang nhiet o nay la 18,015 cal/mol. o.
6

NANG LNG
La thc o o van ong cua vat chat. ng vi nhng
hnh thai van ong khac nhau cua vat chat chung ta co
nhng hnh thai nang lng khac nhau nh the nang,
ong nang, noi nang.
Hai dang the hien cua nang lng o la NHIET, va
CONG
Lu y: khong co gia tr nang lng bang 0 tuyet oi ma
ch co nang lng bang 0 ng vi mot he quy chieu
chuan nao o.

n v o nang lng
Theo he SI la Joule (J):

E k = 1 mv 2 = 1 (2 kg )(1 m/s )2
2

= 1 kg m 2 / s 2
=1J
oi khi dung n v calorie:
1 cal = 4.184 J
n v Calory dinh dng (Cal) (nutritional Calorie):
1 Cal = 1000 cal = 1 kcal
8

NHIET
Nhiet (q) la thc o s chuyen ong hon
loan ( chuyen ong nhiet) cua cac tieu
phan tao nen chat hay he.

CONG
Cong (w) la thc o s chuyen ong co trat t
va co hng cua cac tieu phan theo hng cua
trng lc
CONG (W) = tch cua lc (F)tac dung len vat
lam vat di chuyen mot quang ng d
w=Fd

10

NOI NANG
Noi nang (U) (Internal Energy) cua he la nang
lng co san , an dau ben trong he , bao gom
nang lng chuyen ong tnh tien , chuyen
ong quay cua cac phan t , chuyen ong
quay va chuyen ong giao ong cua cac
nguyen t va nhom nguyen t ben trong phan
t va tinh the, chuyen ong cua electron trong
nguyen t , nang lng ben trong hat nhan.

11

Nang lng cua he: bao gom tong cua


ong nang,
g, The nang,
g, va Noi nang cua
he.
oi vi cac phan ng hoa hoc, s bien
oi ong nang va the nang cua he la
khong ang ke do o ta ch quan tam
en Noi nang.

12

NGUYEN LY TH NHAT CUA NHIET ONG HOC

Neu trong qua trnh nao o ma co mot


dang nang lng a mat i th thay cho no
phai co mot dang nang lng khac xuat
hien vi lng tng ng nghiem ngat.
(nh luat bao toan nang lng)

13

NGUYEN LY TH NHAT CUA NHIET ONG HOC

Moi lien he gia Nhiet va Cong


Nang lng khong t sinh ra va khong t mat i
Nang lng cua (he thong + moi trng) la mot
hang so
Khi mot he b bien oi (vat ly hay hoa hoc), noi
nang cua he thay oi tuy thuoc vao lng nhiet va
cong he trao oi vi moi trng. :
DU = q + w

14

Qui c
ve dau

q:
+ khi he thu nhiet t moi trng ngoai,
khi he toa nhiet ra moi trng ngoai
w:
+ khi he b moi trng ngoai tac dung len cong
w,
khi he tac dung cong w len moi trng ngoai.

15

16

Cong gian n
Cong w khi he chuyen t trang thai 1 sang
trang thai 2 se la :

w = - PV = - P ( V2 V1)
Trong o P la ap suat cua he , V1 la the tch
cua he trang thai 1 , V2 la the tch cua he
trang thai 2.

17

Qua trnh ang tch (


(v=0)
Trong trng hp cac qua trnh dien ra ieu
kien the tch khong oi
(V = const) th w = 0 , suy ra:

qv = U = U2 U1

Toan bo nhiet nang ma he thu vao trong qua


trnh ang tch dung e lam tang noi nang cua
he.
18

Qua trnh ang ap (P=const)


w= -PV do o:

qp = U + PV =( U2 U1) + P (V2 V1) =

(U2 + PV2 ) (U1 + PV1)


Ngi ta at :
H = U + PV
Va goi H la Enthalpy. Vay enthalpy la mot
ham phc tap gom noi nang (U) cua he cong
vi tch ca the tch (V) cua he va ap suat (P)
at tren he.
19

20

ENTHALPY
Khi cung cap cho he mot lng nhiet q th trong trng
hp tong quat nhiet nang nay se c dung e lam tang
noi nang ( phan noi nang tang them ky hieu la U) va e
thc hien cong w chong lai cac lc ben ngoai tac dung
vao he.
nh luat th nhat cua nhiet ong hoc co the bieu dien
bang bieu thc toan hoc sau :

q = U - w = ( U2 U1) w
Trong o , cong w oi vi cac qua trnh (chu yeu la cong
chong ap suat ben ngoai) , U1 la noi nang cua he trc
khi c cung cap nhiet , U2 la noi nang cua he sau khi a
c cung cap nhiet
21

ENTHALPY
Goi H1 la enthalpy cua trang thai ban au cua he
, H2 la enthalpycua trang thai cuoi cung cua he
th chung ta thu c cong thc

qp = H2 H1 = H

Nh vay H la hieu ng nhiet cua cac qua trnh


hoa hoc trong ieu kien ap suat khong oi ( ieu
kien ang ap).

22

ENTHALPY
Neu trong qua trnh he thu nhiet cua moi trng th
Enthalpy cua he tang len tc la
H2 > H1  H = H2 H1 > 0
Neu trong qua trnh he toa nhiet ra moi trng th
Enthalpy cua he giam xuong tc la
H2 < H1  H = H2 H1 < 0
V du:
C + O2 = CO2 H = -396 kJ  phan ng toa nhiet
2 HCl = H2 + Cl2 H = +184 kJ  phan ng thu nhiet

23

MOI QUAN HE GIA ENTANPI VA NOI NANG.


oi vi nhng qua trnh ch co chat ran va long tham
gia th ai lng V co gia tr khong ang ke , do o
khi nhng qua trnh nay c thc hien ap suat thap
th :

H U

Cong thc tren cho thay nhiet truyen cho chat ran va
long chu yeu chuyen thanh noi nang ma khong sinh
cong, tc la chu yeu lam tang nhiet o cua he.

24

MOI QUAN HE GIA ENTANPI VA NOI NANG


oi vi nhng qua trnh co chat phan ng hay san pham
phan ng the kh th H va U co the khac xa nhau.
Vi chat kh :

PV = nRT
Trong o n la hieu so phan t gam cua cac san pham kh
vi so phan t gam cua cac chat kh tham gia phan ng .
Nh vay :

= U + nRT

T ay , khi n = 0 th H = U , nhng khi n 0 th H


U.
25

Enthalpy
DH = Hcuoi - Hau = qP

26

NGUYEN LY TH NHAT CUA NHIET ONG HOC

Qua trnh thu nhiet va toa nhiet


Thu nhiet:: hap thu nhiet t moi trng.
Vd: qua trnh bay hi cua chat long

Toa Nhiet: toa nhiet ra moi trng


Vd: Hoa tan H2SO4 trong nc
Phan ng chay cacbon

27

Entanpi cua phan ng hoa hoc


CH4(g) + 2O2(g) CO2(g) + 2H2O(g) H = -802 kJ
2CH4(g) + 4O2(g) 2CO2(g) + 4H2O(g)
H = -1604 kJ
CO2(g) + 2H2O(g) CH4(g) + 2O2(g) DH = +802 kJ
H2O(g) H2O(l)DH = -88 kJ
28

Phng phap o nhiet lng

Nhiet lng ke

29

Nhiet lng ke ang ap

DH = qP

qp = -qdung dch
= -(nhiet dung cua dung dch)
(so gam dung dch) DT.

30

Nhiet lng ke ang tch


Bomb Calorimetry

qp = -Cnhiet lng keT

31

TNH TOAN HIEU NG NHIET


CUA PHAN NG HOA HOC

32

NH LUAT HESS
Hieu ng nhiet cua qua trnh
hoa hoc ch phu thuoc vao ban
chat va trang thai cua cac chat
au va san pham cuoi ch khong
phu thuoc vao ng i cua qua
trnh
33

V du:
T Cacbon va Oxy co the ieu che CO2 theo hai cach
Cach 1: ot chay trc tiep cacbon
C (than ch) + O2 (kh) = CO2 (kh) H = -393,5 kJ
Cach 2: tien hanh qua hai giai oan
C (than ch) + O2 (kh) = CO (kh) H1 = -110,5 kJ
CO (kh) + O2 (kh) = CO2 (kh) H2 = - 283,0 kJ
Ta co H = H1 + H2

34

HE QUA CUA NH LUAT HESS


He qua 1:
Nhiet phan huy cua 1 hp chat co gia tr tuyet oi ung
bang nhiet hnh thanh cua hp chat o nhng ngc dau.
V du:
H2 (kh) + O2 (kh) = H2O (long) co H = -268 KJ
Vay nhiet hnh thanh cua H2O la H0f = - 268 KJ/mol
Nhiet phan huy cua H2O (long) thanh H2 (kh) + O2
(kh) la +268 KJ/mol

35

H1 = H2 + H3
36

e s oi chieu c thong nhat ngi ta chon nhng


ieu kien sau ay la ieu kien chuan:
 Ap suat c chon la 1 atm =760 mm Hg (hoc 1 bar
=105Pa v ap suat nay neu nhiet o u cao kh co
the xem nh ly tng)
 Cac chat c lay trang thai nguyen chat va ben
nhat 298,15 K va 1 atm.
Hau het cac d lieu nhiet ong c ghi nhan tai
nhiet o 298 K (chnh xac hn la 298,15 K). Tuy
nhien nhiet o khong c bao gom trong khai niem
trang thai chuan. Chung ta co the thiet lap trang thai
chuan bat c nhiet o nao.
37

Phng trnh nhiet hoa hoc:


Mot phng trnh nhiet hoa hoc phai bao gom:
Phng trnh phan ng hoa hoc
Trang thai hoa chat ( ran, long, kh,)
ieu kien th nghiem ( nhiet o, ap suat,)
Nhiet lng trao oi trong phan ng qp hay qv.
Chu y: Nhiet lng trao oi trong phan ng bao gi
cung tng ng vi gia thiet la phan ng xay ra hoan
toan khong kem theo phan ng phu.

38

V du:
C (r) + 1/ 2 O2 (k) CO(k) Ho298K=-110.5 kJ
ngha la 1 mol cacbon ran tac dung vi mol oxygen
tao 1 mol kh monoxyt cacbon; Nhiet phan ng 1 bar,
298.15 K la 110.5 kJ ( nhiet phan ng toa ra la 110.5
kJ).

39

Enthalpy mol chuan thc ( sinh nhiet mol, nhiet tao


thanh mol chuan-heat of formation) Hof
Enthalpy mol chun thccua mot hp chat la hieu ng
nhiet cua phan ng tao thanh 1 phan t gam (1 mol) chat
o t cac n chat ben ieu kien tieu chuan.
Lu y: ngi ta quy c
 Enthalpy (H0f) cua cac n chat ben ieu kien tieu
chuan co gia tr bang 0.

40

4C (r) + 6 H2 (k) + O2 (k) 2 C2H5OH(l)


Ho= -555,38 kJ

Vay: Hof (C2H5OH,l) = -555,38 kJ / 2 mol

= -277,69 kJ.mol-1

41

NHIET TAOTHANH (H0f)


Nhiet tao thanh cua cac n chat ben = 0

42

Thieu nhiet mol chuan (nhiet ot chay-heat of


combustion) Hoc
Thieu nhiet mol chuan (nhiet ot chay) la hieu ng nhiet
cua phan ng ot chay hoan toan 1 mol chat bang oxygen
ieu kien chuan.
C6H12O6 (aq) + 6 O2 (k) 6 CO2(k)
+ 6 H2O(k)

Ho =-2816 kJ
Nhiet ot chay cua ng glucoz la:

Hoc =-2816 kJ.mol-1


Lu y: Trong phan ng chay hoan toan cua cac hp chat
hu c, carbon tao thanh CO2 , Hydro tao thanh H2O, Nit
tao thanh N2
43

Xet phan ng :
C (r) + O2 (k) CO2(k)
Ho298 K =-393.5 kJ
Vay nhiet ot chay cua cacbon tai ieu kien chuan va
nhiet o 298 K la
(Hoc)298 K [C(r)] = -393.5 kJ.mol-1
Xet phan ng :
CO (k) + 1/2 O2 (k) CO2(k)
Ho298 K =-283.0 kJ
Vay nhiet ot chay cua monoxyt cacbon tai ieu kien
chuan va nhiet o 298 K la
(Hoc)298 K [CO(k)] = -283.5 kJ.mol-1
44

Tnh toan Nhiet phan ng Hor bang nhiet


tao thanh Hof
He qua 2 (nh Luat Hess)
Hieu ng nhiet cua phan ng hoa hoc bang
tong nhiet hnh thanh cua cac san pham tr i
tong nhiet hnh thanh cua tac chat
Hor = n
Hof san pham - n
Hoftac chat
45

Tnh toan Enthalpi phan ng bang enthalpi


hnh thanh
Ap dung nh luat Hess

Hp = H1 + H2 + H3

46

Tnh toan Nhiet phan ng Hor bang nang lng

lien ket

Hor = Nang lng t noi - Nang lng rap noi


V du: Tnh Hor cua phan ng
C2H4 (k) + H2 (k) C2H6(k)
Hor=?
Hor=1 mol EH-H + 1 mol EC=C + 4 mol EC-H
(6 mol EC-H +1 mol EC-C)
=1mol(435 kJ.mol-1)+1mol(598 kJ.mol-1)
-2 mol(416 kJ.mol-1)-1 mol(356 kJ.mol-1)
= -155 kJ
So vi ket qua tnh t enthalpy mol chuan thc:
Hor =1 mol Hof, C2H6(k) 1 mol Hof, C2H4(k)
=-84.67 kJ- 52,28 kJ
= -136.95 kJ. Vay ket qua nao ang tin cay hn?

47

CAC NGUON NANG LNG


TRONG T NHIEN

48

THC PHAM
Thc pham cung cap nang lng cho con ngi chu yeu
dang cacbonhydrat (gao, bot m) va m.
Trong c the, cacbonhydrat b chuyen hoa thanh ng
glucoz. ng cung cap nang lng cho c the qua phan
ng:
C6H12O6 (aq) + 6O2(g) 6CO2 (g)+ 6H2O(l)
DH = -2816 kJ
Hoc (C6H12O6, aq) =?
Nang lng d tr trong c the di dang m. M cung
cap nang lng cho c the qua phan ng:
2C57H110O6 + 163O2 114CO2 + 110H2O
DH = -75,520 kJ Hoc = ?
49

Gia tr nang lng cua mot so thc pham

50

CAC DANG NHIEN LIEU THONG DUNG

51

Gia tr nang lng cua mot so dang nhien lieu

52

Chieu xay ra cua cac bien oi t


nhien. Nguyen ly II cua nhiet ong
hoc. Entropy S

53

Trong phan trc chung ta a tra li cau hoi:" Neu mot


phan ng hoa hoc t xay ra no se toa nhiet hay thu
nhiet?"
Nhng con mot cau hoi c ban hn na la:"Neu e t
nhien, khong co s tac ong nao t moi trng, lieu mot
phan ng co xay ra hay khong?"
V du:
Phan ng CH4 + O2 CO2 + H2O tai sao
trong t nhien khong thay chieu ngc lai?
Vay: mot bien oi t nhien th co HNG XAC NH

54

Bien oi t nhien (spontaneous change)


 La mot bien oi xay ra c mot cach t nhien ma
khong can tac ong cua yeu to ben ngoai.
 Mot bien oi t nhien khong nhat thiet phai xay ra
nhanh.
 Chieu cua bien oi t nhien co the phu thuoc vao
nhiet o ( Tai T>0oC, nc a hoa long t nhien. Tai
T<0oC, nc hoa ran t nhien
 Trong mot bien oi t nhien, ng bien oi cua san
pham va tac chat la bien oi bat thuan nghch
(irreversible)

55

56

Vay
Ch da vao s bien oi noi nang (hay Enthalpy
H) th khong the tien oan c chieu phan
ng.
e tien oan chnh xac chieu hng cua phan
ng ta can phai xem xet mot yeu to na o la
O MAT TRAT T cua he (c the hien qua
gia tr ENTROPY ky hieu S)

57

58

59

60

NGUYEN LY 2
Trong ieu kien nang lng khong oi, he co
khuynh hng chuyen t trang thai co o mat trat
t thap sang trang thai co o mat trat t cao hn.
Hay:
Khong the co qua trnh t chuyen nang lng t
vat the co cac tieu phan chuyen ong trat t sang
vat the co cac tieu phan chuyen ong kem trat t
hn.

61

ENTROPI
 Entropi S la thc o o hon loan cua trang thai cua
he thong
 Bien oi xay ra t nhien th i kem vi s tang
entropy
 Thng th s gia tang entropy cua mot qua trnh se
di cung vi s giam entropy cua qua trnh khac
nhng s gia tang la lan at
 Entropy la mot ham trang thai
 Cho 1 he thong: S = Sfinal - Sinitial.
Neu S > 0 he thong mat trat t hn

S < 0 he thong trat t hn

62

 Trong nhiet ong hoc, s hon loan cua mot he thong


c o bang entropy S.
 Neu nh noi nang U xac nh lng cua nang lng th
entropy S xac nh nang lng nay c cat gi ra sao.
 Entropy thap ngha la t hon loan, entropy cao ngha la
hon loan nhieu.
 Khong co khai niem entropy am tc entropy luon luon
>=0.

63

Entropy cua mot chat co the tang bang hai cach:


 Tang bang cach cung cap nhiet dan en gia tang
chuyen ong tc la tang s hon loan cua cac phan t.
 Tang bang cach cung cap nhieu cho hn e cac phan
t co the phan tan de dang hn.

64

Mot so quy tac e danh gia s bien thien cua entropy S


trong cac qua trnh hoa hoc:
 So tang (So>0) khi cac chat chuyen t trang thai ran
sang long hay kh.
V du:
H2O (r) H2O (l)
So>0
 So tang (So>0) khi mot chat ran hay long hoa tan vao
nc hay dung moi.
 So giam (So<0) khi mot chat kh hoa tan vao nc hay
dung moi.
 So tang khi M (khoi lng phan t) tang.
V du:
SoO2 < SoO3

65

 So giam chat ran mang lien ket cong hoa tr, So


tang khi lien ket co mot phan tnh kim loai.
V du:
So C(diamond) < So C(graphite)
 So tang ty le vi o yeu va o mem cua lien ket
gia cac nguyen t.
 So tang theo o phc tap cua phan t.

66

Tnh chat cua entropi


1. Moi chat co gia tr entropi rieng cua mnh , phan t cang
phc tap th entropi cang ln.
2. Entropi cua moi chat 0 K eu bang 0 v chung ch con
mot trang thai sap xep duy nhat (W=1).
3. Entropi cua cac chat tang theo s tang cua nhiet o.
4. Entropi la mot ham trang thai do o s tang entropi cua
mot qua trnh tnh theo cong thc:
Sor = nSsan pham - nStac chat

67

Entropy mol chuan th


thc (S0298)
La gia tr Entropy cua 1 mol chat o ieu kien
ieu kien tieu chuan co ap suat 1 atm (760 mm
Hg), va nhiet o bang 25oC (298.15K)
n v tnh cua S0298 la cal/mol.K hoac J/mol.K
Gia tr nay co the tra cu c t cac SO TAY
HOA HOC.

68

V du
Tnh S0298 cua phan ng
C (than ) + O2 (kh) = CO2 (kh)
Biet gia tr Entropy cua cac chat nh sau
Chat
S

298

C (than )
(Cal/ mol. o K) 1.37

O2 (kh)

CO2 (kh)

49

51.06

S0 = 1mol x S0(CO2) [1 mol x S0(C) + 1 mol x S0(O2)]


S0 = 1mol x 51.06 Cal/ mol. o K [1 mol x 1.37 Cal/ mol. o K + 1
mol x 49 Cal/ mol. o K
S0 = 0.69 Cal/ o K
Nh vay o mat trat t cua he tang len sau phan ng.
69

Anh hng cua moi trng:


Stong cong = She thong + Smoi trng
 Smoi trng ty le thuan vi lng nhiet toa ra t he
thong (-H) va ty le nghch vi nhiet o T. Tai ap
suat khong oi, ta co the viet :

Smoi trng= -H/ T


tc la:
Stong cong = She thong- H/ T

70

V du:
Phan ng 2 Mg (r) + O2 (k) 2 MgO(r)
co Sor = -217 J.K-1.mol-1 <0
Tuy nhien phan ng van xay ra c v Hor<<0 (Hor=1202 kJ.mol-1). Ta co:
Stong cong = She thong - H/ T

= -217 J.K-1.mol-1+ 1202.103 J.mol-1/298 K

= 3.81.103 J.K-1.mol-1>0

71

Nguyen ly II cua nhiet ong hoc cung co the c


phat bieu nh sau

" Mot bien oi t nhien th kem theo


s tang tong entropy cua he thong va
moi trng cua no."

72

Giai thch khai niem entropy mc o phan t


(The Molecular Interpretation of Entropy)

There are three atomic modes of


motion (chuyen ong):
Translation-tnh tien (the moving

of a molecule from one point in


space to another),

Vibration

dao

ong

(the
shortening and lengthening of
bonds, including the change in bond
angles),

Rotation - xoay (the spinning of a


molecule about some axis).

73

 Energy is required to get a molecule to translate, vibrate


or rotate.
 The more energy stored in translation, vibration and
rotation, the greater the degrees of freedom and the
higher the entropy.
 In a perfect crystal at 0 K there is no translation, rotation
or vibration of molecules. Therefore, this is a state of
perfect order.
 Third Law of Thermodynamics: the entropy of a perfect
crystal at 0 K is zero.
 Entropy changes dramatically at a phase change.
74

75

Nang lng t do G (Free Energy)


Stong cong = She thong- H/ T
Hay: -TStong cong = H - TShe thong

Biu dien khai niem bien oi cua entropy tong bang mot
G = ai lng goi la nang lng t do Gibb:
TStong cong (*)
Ta co:
G = H - TS
Nh vay, thay v xem xet s bien oi cua entropy tong
cong cua ca he thong va moi trng xung quanh, nay ta
ch xet s bien oi cua nang lng t do G cua ban than
he thong e d oan mot bien oi co xay ra t nhien hay
khong.
76

Dau tr (-) * cho thay nang lng t do giam


khi entropy tong cong tang. Nh vay, tai ap suat
va nhiet o khong oi, chieu cua mot bien oi t
nhien la chieu lam giam nang lng t do.

77

Bien oi enthalpy
Bien oi entropy Bien oi xay ra t nhien?
--------------------------------------------------------------------------------------------Toa nhiet (H<0)
Tang (S>0)
Co, G<0
Toa nhiet (H<0)
Giam (S<0)
Co, neu |TS| < |H|,
G<0
Thu nhiet (H>0)
Tang (S>0)
Co, neu TS> H,
G<0
G<0
Thu nhiet (H>0)
Giam (S<0)
Khong, G>0
_______________________________________________________

78

V du: Qua trnh ong ac cua nc tai 0oC(273.15 K)


va 1 atm co
H = -Hnc = -6.00 kJ.mol-1
S = -Snc = -21.97 J.K-1.mol-1= -21.97.10-3 kJ.K1.mol-1
The cac gia tr tren vao bieu thc cua G:
G = H - TS
Ta co:
G = -6.00 kJ.mol-11- {(273.15 K)
(-21.97.10-3 kJ.K-1.mol-11)}

= 0.00 kJ.mol-1
Nh vay: Mot phan ng can bang tai nhiet o va ap
suat khong oi co G=0
ieu nay cho phep ta d oan c nhiet o soi, nhiet
o nong chay cua cac chat.
79

Nang lng t do chuan thc Gof


(standard free energy of formation)
La bien thien nang lng t do cua qua trnh tao thanh 1
mol chat ieu kien tieu chuan (250C, 1 atm) xuat phat
t cac n chat ben.
n v cua G0f la Kcal/mol hoac KJ/mol
Cac n chat ben ieu kien tieu chuan co G0f = 0
Gia tr G0f cua cac chat c xac nh bang thc
nghiem.
Co the tra cu cac ai lng G0f trong cac so tay hoa
hoc.

80

Tnh G cua cac phan ng hoa hoc t G0298 cua cac hp


chat

G = G
san pham - G
tac chat
V du: tnh G0 cua phan ng
C (than ) + O2 (kh) = CO2 (kh)
Biet gia tr Entropy cua cac chat nh sau
O2 (kh)
Chat
C (than )

CO2 (kh)

G0298

-94.25

(KCal/ mol).

G0 = 1mol x G0(CO2) [1 mol x G0(C) + 1 mol x G0(O2)]


G0 = 1mol x 94.25 KCal/ mol [1 mol x 0 KCal/ mol + 1 mol x 0 Kcal/ mol
G0 = -94.25 Kcal
Nh vay phan ng t xay ra theo chieu thuan.

81

 Nang lng t do chuan thc Gof chnh la thc


o o ben tng oi cua mot hp chat so vi cac
nguyen to tao thanh no.
 Neu Gof <0 tai mot nhiet o xac nh th co ngha
la cac nguyen to co khuynh hng t nhien tao
thanh hp chat tai nhiet o o tc tai ieu kien
chuan hp chat nay la ben hn cac nguyen to tao
thanh nen no.
 Con neu Gof >0 th ieu ngc lai se xay ra, hp
chat co khuynh hng t nhien la phan huy tr lai
thanh cac nguyen to.

82

y ngha cua Gp
Gp c dung lam thc do cho kha nang t
dien bien cua mot phan ng hoa hoc

Gp < 0 qua trnh hoa hoc co kha nang t
dien bien.

Gp > 0 qua trnh hoa hoc khong co kha
nang t dien bien.
Gp = 0 he hoa hoc nam trang thai can

bang.

83

VAI TRO CUA H, S, T OI VI DAU CUA G VA CHIEU


CUA QUA TRNH.

Neu H <0 & S> 0


 G <0
 qua trnh chac chan xay ra theo chieu thuan.
Neu S~0
muon cho G < 0 phai co H <0
 qua trnh t xay ra theo chieu phat nhiet.

84

VAI TRO CUA H, S, T OI VI DAU CUA G VA CHIEU


CUA QUA TRNH.

Neu H < 0 & S <0


Muon cho G <0 th : |H| > |TS|.

 Nhiet o co anh hng manh en chieu cua


qua trnh:
 nhiet o thap : |TS| nho nen de xay ra ieu kien
|H| > |TS|  qua trnh t xay ra theo chieu thuan.
 nhiet o cao : |TS| ln nen de xay ra ieu kien
|H| < |TS|  qua trnh t xay ra theo chieu nghch.

85

VAI TRO CUA H, S, T OI VI DAU CUA G VA CHIEU


CUA QUA TRNH.

Neu H>0 va S>0


Muon cho G<0 th : |H| < |TS|.
 nhiet o gi vai tro quan trong:
 nhiet o cao: |TS| u ln  |H| < |TS|  G
<0  phan ng theo chieu thuan
 nhiet o thap |TS| khong u ln
 |H| > |TS|  G >0  phan ng theo chieu
Nghch

86

VAI TRO CUA H, S, T OI VI DAU CUA G VA CHIEU


CUA QUA TRNH.

Neu qua trnh co H>0 va S <0 th bat ky


nhiet o nao ta cung co G >0  phan ng
khong the xay ra theo chieu thuan ma ch xay ra
theo chieu nghch

87

Tnh hang so can bang K

Ta co:
Gr = Gor + RT lnK
Tai can bang:
0 = Gor + RT lnK
hay
Gor= RT lnK
V du: Tnh Kp tai 25oC cho can bang sau
N2O4 (k)  2 NO2 (k)
Ta co:
Gor = 2 Gor (NO2,k) - Gor(N2O4,k)
= 2 51.31 97.89 kJ.mol-1
= +4.73 kJ.mol-1
Ma
ln Kp = -Gor / RT
= -(4.73 kJ.mol-1/ 2.4790 kJ.mol-1) = -1.91
Suy ra
Kp = 0.15

88

BAI TAP AP DUNG

89

1J
1 erg
1 cal
1 eV
L.atm
cm-1

= 1 N.m= 1 Pa.m3 = 1 kg. m2. s-2


= 10-7 J
= 4,184 J
= 1,6021892 x 10-19 J
= 101,325 J
= 1,986477 x 10-23 J

1 Pa
1 bar
1 atm
1 atm
1 psi

= 1 N.m-2 = 1 kg. m-1. s-1


= 105 Pa
= 101,325 Pa
= 760 torr
= 6897, 7572 Pa
90

R =

8,31441 J.K-1mol-1
8,31441 m3. Pa.K-1.mol-1
0,0831441 L.bar. K-1.mol-1
0,0820568 L.atm.K-1.mol-1

91

Bai 1
Mot qua bong bay cha khong kh co the tch
4,00x106 lt. Cung cap mot lng nhiet 1,3 x 108
J cho qua bong bang cach ot nong th thay qua
bong tang the tch len thanh 4,5 x 106 lt. Hay
tnh s thay oi noi nang cua qua bong biet
rang trong qua trnh gian n qua bong luon chu
mot ap suat khong oi t kh quyen khong kh la
1,0 atm.

92

Li giai

Noi nang U c tnh theo phng trnh: U= q + W

vi q la lng nhiet cung cap vao he : q = 1,3 x 108 J

Cong trong trng hp nay la cong gian n do he tac ong len moi trng
nen:

W = - PV = - 1 atm x (4,5x106 Lit 4,0x106Lit)= -5,0x105 Lit atm

oi n v : 1 Lit atm = 101,3 J ta co

W = -5,0x105 Lit atm x 101.3 J/Lit atm = -5,1x107 J

Vay: U= q + W = 1,3 x 108 J + (-5,1x107 J) = 8x107 J

Nh vay do lng nhiet cung cap vao he ln hn lng cong do he


tac ong len moi trng nen noi nang cua he tang len.

93

Bai 2
Khi 1 lt dung dch Ba(NO3)2 1M 25 0C c tron lan
vi 1 lt dung dch Na2SO4 1M 25oC trong mot nhiet
lng ke ta thay trong nhiet lng ke xuat hien chat ket
tua mau trang BaSO4 ong thi nhiet o cua nhiet lng
ke tang t 250C len ti 28,1oC. Hay tnh s bien oi
entalpi cua qua trnh hnh thanh 1 mol BaSO4 biet rang
dung dch co t trong l1 1g/ml va co nhiet dung rieng la
4,18 J oC-1 g-1. Gia s lng nhiet hap thu bi nhiet
lng ke la khong ang ke.

94

Li giai
Khi tron lan hai dung dch , phan ng xay ra la:
Ba2+(dung dch) + SO42-(dung dch) = BaSO4 (ran)
Do nhiet o cua dung dch tang len nen ay la phan ng toa nhiet; H co dau am
ay la bien oi ang ap do o s bien oi entalpi chnh la hieu ng nhiet cua phan ng:
H = q
ma q = nhiet toa ra bi phan ng = nhiet hap thu bi dung dch = (nhiet dung rieng cua
dung dch)x(khoi lng dung dch)x(o tang tang nhiet o)
nhiet hap thu bi dung dch= (4,14 J oC-1 g-1)x(2 x103 g)x(28,1 oC 25oC) = 2,6 x104 J
Nh vay khi 1 mol BaSO4 c hnh thanh th lng nhiet toa ra la 2,6 x 104 J
Vay: H = - 2,6 x104 J/mol = -26 kJ/mol

95

Bai 3
Khi 2 mol kh SO2 phan ng hoan toan vi 1 mol
kh O2 e tao thanh 2 mol kh SO3 25 oC tai ap
suat khong oi la 1 atm th toa ra mot lng
nhiet la 198 kJ. Hay tnh H va U cho qua trnh
bien oi.

96

Li giai
Bai giai:
So mol kh trc phan ng :
So mol kh sau phan ng:
n = nsau - ntrc = - 1 mol

SO2 +
2 mol
0 mol

O2 =
1 mol
0 mol

SO3
0 mol
2 mol

ntrc = 3 mol
nsau = 2 mol

ieu kien ang ap H= q = -198 kJ (dau the hien qua trnh toa nhiet)
U = q + w
J
RT

Vi w = -PV= n
= nRT = ( 1mol ) 8,3145
(298K ) = 2,48kJ
Kmol
P

Vay: U = q + w = -198 kJ + 2,48 kJ = -196 kJ


Nhan xet U va H khac nhau do co s thay oi ve the tch cua he khi phan ng xay ra
(cong c thc hien t moi trng ngoai vao he)
97

Bai 4
Hay tnh H0 cho phan ng ot chay NH3 nh sau:
4NH3 (k) + 7O2 (k) = 4 NO2 (k) + 6 H2O(l)

98

Li giai
Chat

H0f (kJ/mol)

NH3 (k)

NO2(k)

H2O (l)

Al2O3 (r)

Fe2O3 (r)

CO2 (k)

CH3OH (l)

C8H18 (l)

-46

34

-286

-167

-826

-349

-239

-269

Bai giai:
4NH3 (k)

H0(a)
H0(b) =0

7O2

2N2 (k) + 6 H2 (k)


7 O2 (k)

H0(c)
H0(d)

4NO2 (k)
6H2O (l)

H0phan ng = H0(a) + H0(b) +H0(c) +H0(d)


= 4 (-H0f (NH3)+ ) + 0 + 4(H0f (NO2)) + 6(H0f (H2O))
= H0f (san pham) - H0f (tac chat)
H0phan ng = 6(-286 kJ) + 4(34kJ) 4(-46 kJ) = -1369 kJ

99

Bai 5
Cho cac so lieu sau:
H2 (k) + O2 H2O (l)
H0 = -285,8 kJ
H0 = -76,6 kJ
N2O5 (k) + H2O (l) 2HNO3 (l)
N2 (k) + 3/2 O2 + H2 HNO3 (l) H0 = -174,1 kJ
Hay tnh H0 cua phan ng:
2N2 (k) + 5O2 (k) 2N2O5 (k)
H0 = 28,4 kJ

100

Bai 6
Quy trnh Oswald dung e ieu che HNO3 t NH3 trong cong
nghiep bao gom cac bc sau:
4NH3 (k) + 5O2 (k) 4 NO (k) + 6H2O (k)
2NO (k) + O2 (k) 2 NO2 (k)
3NO2 (k) + H2O (l) 2 HNO3 (dd) + NO (k)
a) Hay tnh H0 cho moi qua trnh tren da vao gia tr H0f
cua cac hp chat (tra c trong so tay hoa hoc)
b) Viet phan ng tong quat cua qua trnh ieu che tren. Qua
trnh tong quat nay toa nhiet hay thu nhiet?
a. H01 = -908kJ ; H02 = -112 kJ ; H03 = -140 kJ ; b. toa nhiet

101

Bai 7
Xet cac qua trnh bien oi sau:
a) H2O (k) H2O (l)
b) H2 (k) + Cl2 (k) 2HCl (k)
c) 2H2 (k) + O2 (k) 2H2O (k)
d) Xe (k) + F2 (k) XeF2 (r)
e) NiCl2.6H2O (r) NiCl2 (r) + 6H2O (k)
f) CO2 (r) CO2 (k)
ieu kien ap suat khong oi, qua trnh naoco s tac ong
cong t he en moi trng ngoai? Qua trnh nao nhan cong
t moi ttrng ngoai? Qua trnh nao khong co s thc hien
cong?
102

Bai 8
D oan dau cua S0 cua cac phan ng sau:
a) CaCO3 (r) CaO (r) + CO2 (k)
b) 2SO2 (k) + O2 (k) 2SO2 (k)

103

Bai 9
nhiet o nao th qua trnh sau t dien ra 1atm:
Br2 (l) Br2 (k)
Biet qua trnh nay co
H0 = 31,0 kJ/mol va S0= 93,0 J/mol.o

104

Bai 10
Cho cac so lieu sau 25 oC, 1 atm:
G0 = -397 kJ
C (kim cng) + O2 (k) CO2 (k)
C (than ch) + O2 (k) CO2 (k) G0 = -394 kJ
Hay tnh G0 cua qua trnh
C (kim cng) C (than ch)
T o cho biet than ch hay kim cng la dang thu hnh ben
hn cua Cacbon?

105

Bai 11
Phan ng nao sau ay co the t xay ra ieu kien chuan
25oC, 1atm:
a) 2CH3OH (l) + H2O (l) C2H5OH (l)
b) O2 (k) + H2(k) H2O (l)
c) CO (k) + 2H2 (k) CH3OH (l)
d) NO (k) + O3 (k) NO2 (k) + O2 (k)

106

Bai 12
Tnh S0 ; H0; G0 cho phan ng sau
CaCO3 (r) CaO (r) + CO2 (k)
Phan ng nay se t dien ra nhiet o nao?

107