19/09/2016

TEMA II: REACCIONS QUMIQUES

Reaccions qumiques i equaci qumica. Estequiometria (4.1 i 4.2)
Estequiometria de les reaccions en soluci. (4.3, 13.1 i 13.2)
Reactiu limitant. Rendiment duna reacci. (4.4 i 4.5)
Reaccions consecutives, reaccions simultnies i reacciones netes (4.5)
Solucions aquoses: electrlits forts i febles (5.1)
Reaccions de precipitaci: compostos solubles i insolubles (5.2)
Reaccions cid-base: cids i bases forts i febles i neutralitzaci (5.3)
Reaccions redox: semi-reaccions i igualaci de reaccions en medi bsic i
cid (5.4 i 5.5)
A
Agents
t oxidants
id t i reductors
d t
(5 6)
(5.6)
Estequiometria en les reaccions en dissoluci aquosa i valoracions (5.7)
Bibliografia:
llibre de text captols 4 i 5 i apartats 13.1 i 13.2

CHEMICAL REACTIONS

When a chemical reaction takes place, reactants

are converted to products
products.
This is often accompanied by a visual effect:

a color change
a precipitate formation
a gas evolution
a heat absorption or evolution

Sometimes none of these evidences can be observed.

Analysis of the composition of the sample is required

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CHEMICAL REACTIONS
2 NO + 1 O2 2 NO2

Total masses of reactants and products are the same,

as well as the number of atoms in both sides!!

CHEMICAL REACTIONS
BALANCING EQUATION STRATEGY:
Balance elements that occur in only one compound
on each side first.
Balance free elements last.
Balance unchanged polyatomics (or other groups of
atoms)) as g
groups.
p
Fractional coefficients are acceptable and can be
cleared at the end by multiplication.

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CHEMICAL REACTIONS
BALANCING EQUATION. PRACTICE:

2 FeS(s) + 7/2 O2(g)

NH3(g) + O2(g)

Fe2O3(s) + 2 SO2 (g)

N2(g) + H2O(g)

H3PO4((aq)
q) + CaO(s)
( )

Ca3((PO4)2((s)) + H2O(l)
()

C6H14O4(l) + O2(g)

CO2(g) + H2O(l)

State of reagents and products are often

indicated in chemical equations

CHEMICAL REACTIONS. STOICHIOMETRIC

CALCULATIONS
Relating the numbers of moles of reactants and products
When potassium chlorate is heated, it decomposes in
potassium chloride and oxygen. How many moles of O2 are
produced in the decomposition of 1.80 mol of potassium
chlorate?
Answer: 2.70 mols of O2
What is a conversion factor?
How many moles of water are produced by reacting 2.72 mol
of hydrogen in an excess of O2? Answer: 2.72 mols of H2O
What is a limiting reagent?

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CHEMICAL REACTIONS. STOICHIOMETRIC

CALCULATIONS
An alloy used in aircraft structures
consists of 93.7% Al and 6.3% Cu
by mass
mass. The alloy has a density
of 2.85 g/cm3. A 0.691 cm3 piece
of the alloy reacts with an excess
of HCl(aq). If we assume that all
the Al but none of the Cu reacts
with HCl(aq), producing aluminum
chloride and hydrogen, what is the
mass of H2 obtained?

Answer: 0.103 mols of H2

CHEMICAL REACTIONS. STOICHIOMETRIC

CALCULATIONS
Which is the limiting reagent?
In aqueous solution magnesium chloride reacts with silver nitrate to form
a precipitate of silver chloride and magnesium nitrate. How many grams
of silver chloride are formed by reacting 5.0 g of magnesium chloride
and 6.0 g of silver nitrate?
Mw (g/mol)

95,21

169,87

MgCl2(aq) + 2AgNO3(aq)
Moles reagents

5,310-2

3,510-2

Moles products

3,610-2

3,510-2
2

= 1,810-2 moles Mg(NO3)2

2 AgCl(s) + Mg(NO3) 2(aq)

3,510-2

5,310-2 -

3,510-2
2

1,810-2

= 3,610-2 moles MgCl2

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CHEMICAL REACTIONS
CHEMICAL REACTIONS IN SOLUTION
Close contact within atoms, ions and molecules is
necessary for a reaction to occur
occur. This happen when at
least one reagent is gas, liquid or is in solution.
A solution is composed by:
Solvent:
Determines the state of matter in which the solution exists.
Is the largest component
component.
Often is water; these are called aqueous (aq) solutions.
Solutes:
materials dissolved by the solvent.

CHEMICAL REACTIONS
TYPES OF SOLUTIONS

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CHEMICAL REACTIONS
CHEMICAL REACTIONS IN SOLUTION: MOLARITY
M l it (M) = Amount of solute (mol solute)
Molarity
Volume of solution (L)
If 0.40 mol of glucose are dissolved in enough water to
make 0.50 L of solution the concentration is:
0.40
40 moll glucose
l
cglucose = 0
= 0.80 M glucose
0.50 L

CHEMICAL REACTIONS
PREPARING A SOLUTION (MOLAR)

a) weigh the solid sample.

b) dissolve it in a volumetric flask partially filled with solvent.
c) carefully fill to the mark.

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CHEMICAL REACTIONS
PREPARING A SOLUTION BY DILUTION
We want to prepare exactly 0.2500 L (250,0 mL) of an 0.250
M K2CrO
C O4 solution
l ti in
i water.
t
What
Wh t mass off K2CrO
C O4 should
h ld we
use?
Answer: 12.1g
A particular analytical chemistry procedure requires 0.0100 M
K2CrO4. What volume of 0.250 M K2CrO4 should we use to
prepare 0.250 L of 0.0100 M K2CrO4? Answer: 10.0 mL

CHEMICAL REACTIONS
OTHER FORMS TO EXPRESS CONCENTRATION
mass % (m/m): (solute mass / solution mass) 100
10 g of KCl dissolved in 90 g of water makes 10 % KCl m/m aqueous solution
10 g of Ag dissolved in 40 g of Cu makes a 20% Ag m/m solution in Cu.
widely used in industry

volume % (v/v): (solute volume/ solution volume) 100

12 mL of ethanol in 100 mL of wine makes 12% v/v solution
very often used with liquid solutes

mass/volume % (m/v): (solute mass/ solution volume) 100

3 g of NaCl in 100 mL of solution
very often used in medicine and pharmacy

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CHEMICAL REACTIONS
OTHER FORMS TO EXPRESS CONCENTRATION
ppm (parts per million): g of solute/106 g of solution

often is used in very dilute aqueous solutions (d 1.000g/L), then:

15 mg of Cl- in 1.0 L of water makes a 15 ppm chloride solution in water.
used for instance o measure ions in waters (natural, drinking, etc)

ppb (parts per billion): g of solute/109 g of solution

often is used in very dilute aqueous solutions (d 1.000g/L), then:

3 g of Hg
g in 1.0 L of water makes a 3 ppb
pp mercury
y solution in water.
used for instance to measure contaminants in waters

ppt (parts per trillion): g of solute/1012 g of solution

often is used in very dilute aqueous solutions (d 1.000g/L), then:

4 ng of Pu in 1.0 L of water makes a 4 ppt plutonium solution in water.
used for instance to measure heavy contaminants (radioactive) in waters

CHEMICAL REACTIONS
OTHER FORMS TO EXPRESS CONCENTRATION
(molar fraction): moles of solute/ total moles
a mixture of 1.00 moles of methanol in 9.00 moles of water is
(methanol)= 0.10
some physical properties of solutions are related to

m (molality): moles of solute/kg of solvent

0.20 moles of glucose in 1kg of water makes a 0.20 m
some physical properties of solutions are related to m

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CHEMICAL REACTIONS
Theoretical yield is the expected yield from the limiting
reactant.
Actual yield is the amount of product obtained.
Percent yield =

Actual yield
Theoretical Yield

x 100

When actual yield = theoretical yield the reaction is said to be

quantitative.
Side reactions reduce the percent yield
yield.
By-products are formed by side reactions.
The reaction of 25.0 g of P4 with 91.5 g of Cl2 produces 104 g of PCl3.
Calculate the theoretical yield and the percent yield.

Answer: 93.8%

CHEMICAL REACTIONS:
SIMULTANEOUS REACTIONS
When substances react independently and at the same time
reactions are called simultaneous reactions.
For instance, inside the pistons of a car engine, gasoline
(hexane C6H14 is one the components of gasoline) is mixed with
air (N2+ O2) at relatively high temperature.
In this conditions, oxygen reacts simultaneously with both
hexane and N2 :
C6H14(g) + 19/2 O2(g) 6 CO2(g) + 7 H2O(g) (main reaction)
N2(g) + 2 O2(g) 2 NO2(g) (side reaction)
There is not relation between the stoichiometry of
one and other reaction

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CHEMICAL REACTIONS: MULTISTEP REACTIONS

(SEQUENTIAL REACTIONS)
Multistep synthesis is often unavoidable.
Reactions carried out in sequence are called consecutive
reactions.
ti
The Overall Reaction is a chemical equation that expresses
all the reactions occurring in a single overall equation.
An intermediate is a substance produced in one step and
consumed in another during a multistep synthesis.

CHEMICAL REACTIONS: MULTISTEP REACTIONS

(SEQUENTIAL REACTIONS)
The process to obtain tungsten (W) from the oxide WO3 requires
three steps (the hydrogen obtained in the two first reactions is used to
reduce the oxide in the third reaction):

CH4(g) + H2O (g) CO(g) + 3 H2(g)

CO (g) + H2O (g) CO2 (g) + H2 (g)

WO3 (s) + 3 H2 (g) W (s) + 3 H2O (g)

4 WO3(s) + 3 CH4 (g) 4 W (s) + 3 CO2(g) + 6 H2O(g)

overall reaction
How many moles of methane are needed to obtain one mole
of tungsten?
Answer: 0,75 moles

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TREBALL PERSONAL
Bibliografia:
Reaccions
R
i
qumiques
i
i equaci
i qumica.
i
E
Estequiometria
t
i
t i (4.1
(4 1 i 4
4.2)
2)
Estequiometria de les reaccions en soluci. (4.3, 13.1 i 13.2)
Reactiu limitant. Rendiment duna reacci. (4.4 i 4.5)
Reaccions consecutives, reaccions simultnies i reacciones netes (4.5)

Problemes:
Problemes 1-8

AQUEOUS SOLUTIONS:
ELECTROLYTES AND NON- ELECTROLYTES
Water as solvent (aqueous solutions):
inexpensive
can dissolve a vast number of substances
many substances dissociate into ions
aqueous solutions are found everywhere
seawater
lakes and rivers
drinking waters
living systems

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AQUEOUS SOLUTIONS:
ELECTROLYTES AND NON- ELECTROLYTES
Some solutes can dissociate into
positive and negative ions, allowing the
flow of charges through the solution.

Strong electrolyte dissociates completely

(good electrical conduction)
Weak electrolyte partially dissociates (fair
conductor of electricity)
Non-electrolyte does not dissociate (poor
conductor of electricity)

ELECTROLYTES AND NON- ELECTROLYTES

CH3OH(aq)

MgCl2(s)
Mg2+(aq) + 2 Cl-(aq)

CH3CO2H(aq)
CH3CO2-(aq) + H+(aq)

(non-electrolyte)

(strong electrolyte)

(weak electrolyte)

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ELECTROLYTES AND NON- ELECTROLYTES

SOLVATION: interaction of the solvent with the solute

Hydrated Proton:
H+(aq) or H3O+

Hydrated positive and negative ions:

A+(aq) and B-(aq)
click to see a clip about solvation

PRECIPITATION REACTIONS
AgI(s)
AgNO3(aq)

NaI(aq)

Na+(aq) NO3-(aq)

Soluble ions can combine to form an insoluble compound

that precipitates

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PRECIPITATION REACTIONS
Overall Precipitation Reaction:
AgNO3(aq) +NaI(aq) AgI(s) + NaNO3(aq)
Spectator ions
Complete ionic equation:
Ag+(aq) + NO3-(aq) + Na+(aq) + I-(aq)
AgI(s) + Na+(aq) + NO3-(aq)

Net ionic equation:

Ag+(aq) + I-(aq) AgI(s)

PRECIPITATION REACTIONS
SOLUBILITY AND INSOLUBILITY RULES

Compounds that are soluble:

alkali metal ion and ammonium ion salts
Li+, Na+, K+, Rb+, Cs+,NH4+
nitrates, perchlorates and acetates
NO3- , ClO4- , CH3CO2-

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PRECIPITATION REACTIONS
SOLUBILITY AND INSOLUBILITY RULES

Compounds that are mostly soluble:

chlorides, bromides and iodides (Cl- , Br- and I-)
except those of Pb2+, Ag+, and Hg22+.
sulfates (SO42-)
exceptt those
th
off Ca
C 2+, Sr
S 2+, Ba
B 2+, Pb2+ and
d Hg
H 22+.

PRECIPITATION REACTIONS
SOLUBILITY AND INSOLUBILITY RULES

Compounds that are insoluble:

hydroxides and sulfides (OH- and S2-)
except alkali metals and ammonium salts
except sulfides of alkaline earths
2 and
3)
carbonates
b
t and
d phosphates
h
h t (CO32d PO43except alkali metals and ammonium salts

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ACID-BASE REACTIONS
Svante Arrhenius theory (1884)

ACID from latin acidus

Provide H+(aq) in aqueous solutions

ALKALI from arabic al-qali (ashes of certain plants)

Provide OH-(aq) in aqueous solutions

ACID-BASE REACTIONS
Svante Arrhenius theory (1884)
Acids provide H+(aq) in aqueous solution.
Strong acids completely ionize:
HCl(aq) H+(aq) + Cl-(aq)
Weak acid ionization is not complete:
CH3CO2H(aq)
H+(aq) + CH3CO2-(aq)
Bases provide OH-(aq) in aqueous solution.
Strong bases completely ionize :
NaOH(aq) Na+(aq) + OH-(aq)
Weak bases ionization is not complete :
NH3(aq) + H2O(l)
OH-(aq) + NH4+(aq)

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ACID-BASE REACTIONS
RECOGNIZING ACIDS AND BASES
Acids have ionizable hydrogen ions.
HNO3, CH3CO2H,, HF,, HCN,, H3NH+, H3PO4, etc
Bases have OH- combined with a metal ion.
KOH
or can be identified by chemical equations
Na2CO3(s) + H2O(l) HCO3-(aq) + 2 Na+(aq) + OH-(aq)
COMMON STRONG ACIDS:
HCl
HBr
HI

HClO4
HNO3
H2SO4 (only one H)

COMMON STRONG BASES:

LiOH
NaOH
KOH
RbOH, CsOH

Ca(OH)2
Sr(OH)2
Ba(OH)2

ACID-BASE REACTIONS
NEUTRALIZATION:
REACTION OF ONE ACID WITH ONE BASE
strong acid with strong base

weak acid with strong base

strong acid with weak base

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ACID-BASE REACTIONS
NEUTRALIZATION:
REACTION OF ONE ACID WITH ONE BASE

Mg(OH)2(s) + 2 H+(aq) Mg2+(aq) + 2 H2O(l)

CaCO3(s) + 2 H+(aq) Ca2+(aq) + H2CO3(aq)

H2CO3((aq)
q) H2O(l)
( ) + CO2(g)
CaCO3(s) + 2 H+(aq) Ca2+(aq) + H2O(l) + CO2(g)

REDOX REACTIONS
Redox reactions:
THERE ARE CHANGES in the oxidation states of some
elements
Precipitation and acid-base reactions:
THERE ARE NOT changes in the oxidation states of some
elements

Fe2O3 (s) + 3 CO (g) 2 Fe (l) + 3 CO2 (g)

Fe(III) is reduced to metallic iron Fe(0)
C(II) in CO(g) is oxidized to C(IV) in carbon dioxide
Oxidation and reduction always occur together

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REDOX REACTIONS

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

REDOX REACTIONS
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
O id ti
Oxidation:
Zn(s) Zn2+(aq) + 2 eOxidation state some element increases in the
reaction.
Electrons are on the right of the equation
Reduction:
Cu2+(aq) + 2 e- Cu(s)
Oxidation state some element decreases in the reaction.
Electrons are on the left of the equation

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REDOX REACTIONS
BALANCING REDOX EQUATIONS

Few can be balanced by inspection. Systematic approach required.

The Half-Reaction
Half Reaction (Ion-Electron)
(Ion Electron) Method
Two different approaches: acid (with H+) or base (OH-) media
General strategy: write and balance independently oxidation a reduction
half-reactions and then add them
Steps for reactions in acid media:
- Write the equations for the half-reactions.
Balance all atoms except H and O.
Balance oxygen using H2O.
Balance hydrogen using H+.
Balance charge using e-.
Equalize the number of e-.
Add the half reactions.
Check the balance

REDOX REACTIONS
Balancing the Equation for a Redox Reaction in Acidic Solution.
The reaction described below is used to determine the sulfite ion
concentration present in wastewater from a papermaking plant. Write the
balanced equation
q
for this reaction in acidic solution..

SO32-(aq) + MnO4-(aq) SO42-(aq) + Mn2+(aq)

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REDOX REACTIONS
BALANCING EQUATIONS IN BASIC SOLUTION
OH- appears instead of H+.
Steps:
p
Treat the half-equations as if it were in acid (use H+ and H2O)
Then add OH- to each side to neutralize H+.
Remove H2O appearing on both sides of equation.
Add the half reactions.
Check the balance

Example:
CN-(aq) + MnO4-(aq) NCO-(aq) + MnO2(s)

REDOX REACTIONS
DISPROPORTIONATION REACTIONS
The same substance is both oxidized and reduced.
Some have practical significance
Hydrogen peroxide
2 H2O2(aq) 2 H2O(l) + O2(g)
Sodium thiosulphate
S2O32-(aq) + 2 H+(aq) S(s) + SO2(g) + H2O(l)

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REDOX REACTIONS
OXIDAZING AND REDUCING AGENTS
An oxidizing
g agent
g
((oxidant):
)
Contains an element whose
oxidation state decreases in a redox
reaction
A reducing agent (reductant):
Contains
C t i an element
l
t whose
h
oxidation state increases in a redox
reaction.

REDOX REACTIONS
OXIDAZING AND REDUCING AGENTS:
OXIDATION STATES OF NITROGEN

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STOICHIOMETRY OF REACTIONS IN
AQUEOUS SOLUTIONS: TITRATIONS
Titration
Carefully controlled addition of one solution
to another until the equivalence point
Equivalence Point
Both reactants have reacted completely.
Indicators
Substances which change color at the
equivalence point.

STOICHIOMETRY OF REACTIONS IN
AQUEOUS SOLUTIONS: TITRATIONS
INDICATORS

5.0 mL CH3CO2H
A few drops
phenolpthalein

Add 0.1000 M NaOH

The endpoint:
(equivalence point)

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STOICHIOMETRY OF REACTIONS IN
AQUEOUS SOLUTIONS: TITRATIONS
Sometimes indicators are not needed.
Reagents act as indicators
Standardizing a Solution for Use in Redox Titrations.
A piece of iron wire weighing 0.1568 g is converted to
Fe2+(aq) and requires 26.24 mL of a KMnO4(aq) solution
for its titration. What is the molarity of the KMnO4(aq)?
5 Fe2+(aq) + MnO4-(aq) + 8 H+(aq)
5 Fe3+(aq) + Mn2+(aq) + 4 H2O(l)

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