Slide

Part II: Fundamental laws of chemical
processes
Chapter 1: Thermodynamics of chemical

reactions

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1.1. Principles of heat flow
Almost chemical reactions absorb or release
energy, in the form of heat. It is important to
understand the distinction between thermal energy
and heat.
Heat is the transfer of thermal energy between two
bodies having different temperatures. Speak Heat
flow from a hot object to a cold one.
Thermochemistry is the study of the heat change in
chemical reactions

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1.1.1. System and surroundings
1. The system is that part of the universe on which
attention is focused.
2. The surroundings are the rest of the universe
outside the system.
Example: a sample of solution in contact with a hot plate
The solution is the system
The hot plate and the glass
holding the solution is the
surroundings

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3. There are three types of systems:
An open system can exchange mass and energy,
usually in the form of heat with its surroundings
An open system consist of a quantity of water in an
open container.
A closed system exchanges energy, but does not mass

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An isolated system does exchange neither heat
nor mass with surroundings
If we place the above flask in totally insulated
container, we obtained an isolated system.
1.1.2. Direction and sign of heat flow
Heat (q) has positive value when heat flows from
the surroundings into the system.
Heat (q) has negative value when heat flows out of
the system into the surroundings
Part II: Fundamental laws of chemical

processes
An endothermic process, in which heat flows
from the surroundings into the system
Example: the melting of ice:
H2O(s) H2O(l) q>0
The process absorb heat from the surroundings, the
temperature of surroundings drops as they give up
heat to the system
An exothermic process, in which heat flows from
the system into the surroundings
Example: The combustion of methane
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) q<0
This reaction evolves heat into the surroundings.
The effect of the heat transfer is to raise the
temperature of the surroundings.

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1.1.3. State Properties:
A system can be exist at many diffrent states. The state
of a system can be defined by a set of conditions such as
state properties and state functions.
State properties: Temperature (T), pressure (P),
composition (concentration, moles), volume (V)
State function: its value depends only on the state of
the system, and not on the way by which the system
reached that state.
Example: Internal energy (U), entropy (S), enthalpy (H)
When the system transfers from one state to another,
the change in a state function is different between two
its values in final and initial states.
U=U2-U1; S= S2-S1 H= H2-H1

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1.2. First law of thermodynamics
1.2.1. Internal energy:
Internal energy is the total energy contained in the
system including kinetic energy of particles
movement and potential energy of the attractive
interactions of particles.
* Internal energy is a state function. Its value
depends only on its states, not on the way.
* Internal energy is a extensive property because its
value depends on the mass of material

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1.2.2. Statement of the first law of thermodynamics
Energy can be converted from one form to another,
but cannot be created or destroyed.
When the system transfers from one state to
another, the total of heat and work exchanged with
surroundings equal to the change of internal energy
of the sytem
U = q+ w
If the initial and final states coincide, U =0
For isolated system, q=w=0, U =0

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When the system transfers from state 1 to state 2 by different
ways, anyway the change of its internal energy U = constant,
however, heat and work are changed depending on the way
U = q1+ w1 =q2+w2=q3+w3
Sign of heat and work

The system receives energy from the surroundings, q, w >0
The system give off energy into the surroundingd q, w<0

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1.2.3. Enthalpy (H)
Most chemical reactions occur at constant (usually
atmospheric) pressure
The quantity of heat transferred into or out of a
system as it undergoes a chemical or physical
change at constant pressure qp is defined as the
enthalpy change H of the process.
For reactions, the enthalpy change is equal to the
enthalpy of the products minus the enthalpy of the
reactants
H = Hproducts-Hreactants
Enthalpy is also a state function.

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1.3. The application of the first law of
thermodynamics to chemistry. Entanpy (heat) of
reaction
1.3.1. Standard states
The thermodynamic standard state of a substance
is its most stable form under standard pressure (1
atm) and at some specific temp. (25 oC, 298K)
Examp. Graphite Cgr is the standard state of
carbon
Gaseous diatomic molecule H2 is the standard for
hydrogen

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1.3.2. Standard enthalpy (heat) of reaction
aA + bB = cC + dD
1.3.3. Enthalpy (heat) of formation

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Example:
In a contrast with enthalpy of formation is enthalpy of

decomposition.
Hod(HBrg) = 36.4 KJ.mol-1

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1.4. Hesss law
1.4.1. Statement:
The enthalpy change for a reaction is dependent
only on the initial state and final state, but not on
the intermediate states.
For example: Combustion of Cgr to form CO 2 (two
ways)
Cgr + O2(K)
Ho1
CO2(K)
Ho3
Ho2
CO(K) + 0,5O2(K)
H1= H2+ H3

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1.4.2. Consequense of the Hesss law
1. Hesss law allow to calculate enthalpy changes of
reactions for which the changes could be measured
only with difficulty.
2. Calculate the change enthalpy of reactions

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Example: Calculate Ho 298 for the reaction

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
H0298,f -74,85
-393,51 -285,84
KJ.
mol-1
Ho298,react.= Ho298,f(CO2g) + 2.Ho298,f(H2Ol)Ho298,f(CH4g)= -890,34KJ.mol-1

Example:

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1.5. BOND ENERGIES
1.5.1. Energy of chemical bond
The bond energy (B.E) is the amount of energy released
to form one mole of bonds of the product in the gaseous
state.
H(g)+H(g) H2(g) Horxn = HH-H = -436 KJ.mol-1
The energy of dissociation is the amount of energy,
required to break one mole of bonds in a gaseous
substance to form the gaseously isolated atoms
436 KJ.mol-1 must be absorbed for every mol of H-H
bonds that are broken. This endothermic reaction
(Horxn is positive) can be written:
H2(g) + 436 KJ 2H(g) Horxn = HH-H = +436
KJ.mol-1

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1.5. BOND ENERGIES
Chemical reactions involve the breaking and making of
chemical bonds. Energy is always required to break a
chemical bond and released to form a chemical bond
Often this energy is supplied in the form of heat.
1.5.2. Enthalpy of reaction

A special case of Hesss Law involves the use of
bonds energies to estimate heats of reaction.

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1.5. BOND ENERGIES
A schematic representation of relationship

between bond energies and heat of reaction

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1.5. BOND ENERGIES
Horxn = B.E (products) - B.E (reactans)
Example: Use the bond energy to estimate the heat
of reaction at 298K for the following reaction.
N2(g) + 3H2(g) 2NH3(g)
EN-H = -391 KJ.mol-1; ENN = -945KJ.mol-1; EH-H = -436

KJ.mol-1
Using the bond energy form of Hesss Law

Horxn (298)=-6.(391)+[945+3(436)]= - 93KJ.mol -1

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1.6. THE SECOND LAW OF THEMORDYNAMICS
1.6.1. Spontaneous processes
We observe spontaneous physical and chemical
processes every day:
Waterfall runs downhill, but never up, spontaneously
Heat flows from a hot object to a colder one, but the
reverse never happens spontaneously
Water freezes spontaneously below 0oC and ice melts
spontaneously above 0oC
A piece of sodium metal reacts with water to form
hydroxide and hydrogen gas, however, hydrogen gas
does not react with sodium hydroxide to form water
and sodium
Na + H2O = NaOH + 1/2H2

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A large number of exorthemic reactions are
spontaneous, such as the combustion of methane:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Ho = -890.4
KJ
Or the acid-base neutralization reaction:
H+(aq) + OH-(aq) H2O(l)
Ho = -56.2 KJ
But a solid- to-liquid phase transition
H2O(s) H2O(l)
Ho = 6.01 KJ

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We come to the following conclusion: Exothermicity

favors the spontaneity of a reaction but does not always
The second themordynamics help you to establish
criterion to consider direction of any process.
To make this prediction we need another
themordynamic quantity, which turns out to be
entropy.

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1.6.2. Entropy, S
Entropy is a measure of the disorder of a system. The
greater the disorder of a system, the greater its entropy.
Conversely, the more ordered a system, the smaller its
entropy.
For any substance, the particles in solid state are more
ordered than those in the liq. state, which in turn, are
more ordered than those in the gaseous state. Thus, for the
same molar amount of a substance we can write:
Ssolid < Sliq. << Sgas

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It is possible to determine the absolute

entropy of a substance, something we cannot
do for enthalpy.
Standard entropy is the absolute entropy of
o
a substance at 1 atm and at 25 C.
The units of entropy are J/K or J/K.mol. Entropies
of elements and compounds are all positive.

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Entropy is a state function.

Consider a certain process in which a system
changes from some innitial state to some final state.
The entropy change for the process,
S = Sf-Si, where Sf and Si are the entropies of the
system in the final and initial states, respectively.
If the change results in an increase in disorder,
then Sf > Si or S > 0

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1.6.3. Statement of the 2nd Law of thermodynamics

The connection between entropy and the
spontaneity of a reaction is expressed by the second
law of themordynamics:
The entropy of the universe increases in a
spontaneous process and remains unchanged in an
equilibrium process.

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Since the universe consists of the system and the surr., the
entropy change in the universe (Suniv) for any process is the
sum of the entropy changes in the system (S sys) and in the
surr. (Ssur).
We can express the 2nd law of thermodynamics:
For a spontaneous process: Suniv = Ssys +Ssurr > 0
(2.1)
For an equilibrium process: Suniv = Ssys +Ssurr = 0
(2.2)
For a spontaneous process, the second law says that Suniv
must be greater than zero. For an equilbrium process, Suniv
= 0, so in this case Ssys= -Ssurr

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1.6.4. Entropy changes of the system
To calculate Suniv, we need to know both Ssys and
Ssurr. Let us focus first on Ssys. Suppose that the system
represented by the following reaction:
aA + bB cC + dD
The standard entropy change of reaction Sorxn is given by:
Sorxn = [cSo(C) + dSo(D)]-[aSo(A) + bSo(B)]
(2.3)
a, b, c, d are the stoichiometric coefficients in the reaction.
The standard entropy values of a large number of
compounds have been measured in J.K-1.mol-1

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1.6.5 Entropy changes in the surroundings Ssurr
When exothermic process takes place in the system:
+ the heat transferred to the surr. enhances motion of the
molecules in the surr. So, there is an increase in disorder at
the molecular level and the entropy of the surr. increases.
Conversely, an endothermic process in the system
+ the heat absorbs from the surr. and so decreases the
entropy of the surr.
For constant- P processes the heat change is equal to the
enthalpy change of the system, Hsys. Therefore, the
change in entropy of the surr., Ssys, is propotional to
Hsys:
S
-H

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The change in entropy also depends on temperature.
+ If the temp. of the surr. is high, the molecules are
already quite energetic. Therefore, the absorption of heat
from the system will have little impact on molecular
motion and the resulting increase in entropy will be small.
+ If the temp. of the surr. is low, then the addition of the
same amount of heat will cause a more drastic increase in
molecular motion and hence a larger increase in entropy.
+ From the inverse relationship between Ssurr and
temperature T- the higher the temperature, the smaller
the Ssurr. We can rewrite the above relationship:
(2.4)
H sys
S surr
T

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1.7. GIBBS FREE ENERGY
1.7.1. Establish the spontaneity criterion of reactions

We have to determine the sign of Suniv for a
reaction to consider the direction of reaction
We would need to calculate both Ssys and Ssurr,
however the calculation of Ssurr can be quite difficult.
Therefore we rely on another thermodynamic
function to help us determine whether a reaction will
occur spontaneously if we consider only the system.
From equation (2.1), we know that for a spontaneous
process, we have:
Suniv = Ssys + Ssurr > 0
Substituting Hsys/T for Ssurr we write:
or
TSuniv= -Hsys + TSsys >0

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For convenience, we can change the above equation,

multiplying it throughout by -1:
- TSuniv= Hsys - TSsys < 0
This equation says that for a process carried out at
temperature T, if the changes in entropy and enthalpy of
the system are such that Hsys - TSsys less than zero,
the process must be spontaneous.
To express the spontaneity of a reaction more directly,
we should use another thermodynamic function called
Gibbs free energy (G):
G = H-TS
2.5)
G has units of energy (both H and TS are in energy
units). Like H and S, G is a state function.

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The change in free energy of a system for a
constant-pressure process is:
G= H- TS
We can define the conditions for spontaneity and
equilibrium at constant T and P in terms of G as
follows:
G < 0
The reaction is spontaneous in the
forward direction
G > 0 The reaction is nonspontaneous in the
forward direction. The reaction is spontaneous in
the reverse direction
G = 0
The system is at equilibrium.

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1.7.2. Standard free energy changes
The standard free energy of reaction (Gorxn) is the free
energy change for a reaction when it occurs under
standard-state conditions, when reactants and products in
their standard states. We consider the following reaction:
aA + bB cC + dD
The standard free-energy change for this reaction is
given by:
Gorxn = [cGof(C) + dGof(D)] [aGof(A)+bGof
(B)]
Gof is the standard free energy of formation of a
compound, that is, the free -energy change of reaction
that occurs when 1 mole of the compound is synthesized

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For combustion of graphite:
C(gr) + O2(g) = CO2(g)
Gorxn = Gof(CO2) Gof(Cgr)- Gof(O2)
From the above concept:
Gof(Cgr)= 0 and Gof(O2)=0
The standard free energy of formation of any
element in its stable state from as zero.
Gorxn = Gof(CO2)

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Methods for calculating the standard free energy
change of reactions
1. The calculation of Gorxn from tabulated values of Gof, if
the reaction occurs at 25oC and at 1atm
Example 1: Calculate the standard free energy changes for the
following reactions at 25oC, based on the tabulated values of
Gof:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
Gof,298
-50.8
0
-394.4
-237.2 KJ.mol 1
Gorxn,298 = [Gof,298(CO2) + 2Gof,298(H2O)]-[ Gof,298
(CH4) + 2Gof,298(O2)]
= -394.4 + 2(-237.2) [(-50.8) + 2(0)] = -818 KJ
Gorxn,298 < 0, the reaction is spontaneous at standard
conditions and at 25oC

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o
o
2. The calculation with the equation G = H - TSo,

where the temperature T in kelvins
Example 2: Calculate the free energy change under
standard conditions and at 298K
N2(g) + O2(g) 2NO(g)
Hof, KJ.mol-1
0
0
90.25
So298, J.mol-1.K-1 191.5
205.0
210.7
Horxn,298 = Hof,298(products) - Hof,298(reactants)
= 2Hof,298(NOg) [Hof,298(N2g) + Hof,298(O2g) =
2x90.25 = 180.5 KJ.mol-1
Sorxn,298 = So298(products) - So298(reactants) =
2x210.7 [191.5 + 205.0] = 24.9 J.K-1.mol-1
Now we use the relationship GoT,rxn = HoT,rxn TSorxn
Go298,rxn =180.5 298x0.0249 = +173.1 KJ.mol-1

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1.7.3. The influence of energy and entropy factors on direction of
reaction
G = H-TS, therefore the direction of the reaction depends on
the sign and magnitude of these above factors.
1. If both H and S are positive, then G will be negative only
when the TS term is greater in magnitude than H. This
condition is met when T is larger.
2. If H is positive and S is negative, G will always be positive,
regardless of temperature.
3. If H is negative and S is positive, then G is always be
negative, regardless of temperature.
4. If H is negative and S is negative, then G will be negative
only when TS is smaller in magnitude than H. This condition
is met when T is small.
The temperatures that will cause G to be negative for the first
and last cases depend on the actual values of H and S of the
system. Table 2.1 summarizes the effects of the possibilities just
described.

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Table 2.1. Factors affecting the sign of G in the
relationship G = H- TS
Examples
Reaction is spontaneous at high

temperatures. At low temperatures,
reaction is spontaneous in the
reverse direction
H2(g) + I2(g) 2HI(g)
G is always positive. Reaction is

spontaneous in the reverse direction
at all temperatures
3O2(g) 2O3(g)
G is always negative. Reaction

proceeds spontaneously at all
temperatures
2H2O2(l) 2H2O(l) + O2
Reaction is spontaneous at low

temperatures. At high temperatures,
the reverse becomes spontaneous.
NH3(g) + HCl (g)

NH4Cl(s)
(g)
Chapter 2: Chemical equilibrium

2.8. CHEMICAL EQUILIBRIUM
2.8.1. Basic concepts
2.8.1.1. Reversible reaction:
Few chemical reactions proceed in only one direction, called
one direction reaction.
Most chemical reactions do not go to completion. That is,
when reactants are mixed in stoichiometric quantities, they are
not completely converted to products.
Reactions that do not go to completion and that can occur in
either direction are called reversible reactions.
Reversible reactions can be represented in general terms as
follows:
aA + bB cC + dD

aA + bB cC + dD
Where the capital letters represent formulas and the lowercase
letters represent the stoichiometric coefficients in the balanced
equation.
Double arrow indicates that the reaction is reversible, that is,
both the forward and reverse reactions occur simultaneously.
The substances appear on the left side of the balanced chemical
equation called the reactants, and those on the right side
called the products.
In fact, the reaction can proceed in either direction. When A
and B react to form C and D at same rate at which C and D
react to form A and B, the system is at equilibrium.

2.8.1.2. Chemical equilibrium:
Chemical equilibrium is a state of reversible reaction
Chemical equilibrium is achieved when the rates of the
forward and reverse reactions are equal and the
concentrations of the reactants and products remain
constant.
Chemical equilibria are dynamic equilibria, because
individual molecules are continually reacting, even though
the overall composition of the reaction mixture does not
change.

2.8.2. Equilibrium constant

Consider the reversible reaction:
aA + bB cC + dD
For the reaction at a particular temperature:
c
d
C D
K
Aa B b
Where K is the equilibrium constant. The equilibrium constant K is
defined as the product of the equilibrium concentrations of the
products, each raised to the powder that corresponds its coefficient
in the balanced equation, divided by the product of the equilibrium
concentrations of reactants, each raised to the powder that
corresponds to its coefficient in the balanced equation.

2.8.2.1. Equilibrium constant expressions
* For homogeneous equilibria
The term homogeneous equilibrium applies to reactions in which all
reacting species are in the same phase.
Example: The dissociation of N2O4
N2O4(g) 2NO2(g)
2
The equilibrium constant is:
NO2
Kc
N 2 O4
The subscript in Kc indicate that the concentrations of the reacting species are
expressed in molarity or moles per liter.
Kc is the equilibrium constant calculated by concentrations; the brackets [ ] in
this expression indicate equilibrium concentrations of the substances.

The equilibrium constant has no units. The magnitude of Kc is a
measure of the extent to which reaction occurs. For any balanced
chemical equation, the value of Kc
- is constant at a given temperature;
- changes if the temperature changes;
- does not depend on the initial concentrations
However, the concentrations of reactants and products in gaseous
reactions can also be expressed in terms of their partial pressures.
The pressure P of a gas is directly related to the concentration in mol/l
of the gas; that is, P= (n/V)RT. Thus, for the equilibrium process:
N2O4(g) 2NO2(g)
P 2 NO2
Kp
PN 2O4

In general, Kc is not equal to Kp, since the partial pressures of
reactants and products are not equal to their concentrations.
A simple relationship between Kp and Kc can be derived as
follows. Let us consider the following equilibrium in the gas
phase:
aA bB
Where a and b are stoichiometric coefficients. The equilibrium
constant Kc is given by:
b
B
Kc
Aa

the expression for Kp is
Kp
Pb B
a
P A
Where PA and PB are the partial pressures of A and B

Assuming ideal gas behavior, PAV = nART
PA
n A RT
V
Substituting these relations into the expression for Kp, we obtain

b
n B RT
nB
V
V
B
ba
Kp
( RT )
( RT ) n
a
a
a
A
n A RT
nA

V
V
Kp = Kc(RT)n
Where n = b-a = moles of gaseous products- moles of gaseous
reactants; R-the gas constant given by 0.0821 l.atm/K.mol.
Kp Kc except in the special case in which n = 0

* For heterogeneous equilibria
A heterogeneous equilibrium results from a reversible
reaction involving reactants and products that are in
different phases.
For example, when calcium carbonate is heated in a
closed vessel, the following equilibrium is attained:
CaCO3(s) CaO(s) + CO2(g)
The two solids and one gas constitute three separate
phases. At equilibrium, we might write the equilibrium
constant as:
CaO CO
Kc '
[CaCO3 ]

The terms [CaCO3] and [CaO] are constant. We can simplify the
above equation by writing:
CaCO3 K
[CaO ]
' K c [CO2 ]
where Kc, the new equilibrium constant. Note that the value of
Kc does not depend on how much CaCO3 and CaO are present.
We also can express the euilibrium as Kp = PCO2

The reaction quotient, Q, for the general reaction is given as
follows
For:
aA + bB cC + dD
c
d
C D
Q
Aa Bb
Q is a measure of the progress of the reaction.

When the mixture contains only reactants, the concentrations in the numerator
are zero, so Q = 0.
As the reaction proceeds to the right, the product concentrations (numerator)
increase and the reactant concentrations (denominator) decrease, so Q
increases to an infinitely large value when all reactants have been consumed
and only products remain.
The value of Kc is a particular value of Q that represents equilibrium mixtures
for the reaction.

2.8.3. Relationship between Gorxn
equilibrium constant
and
the
Under standard conditions to predict the direction of the

reaction we used Gorxn
Under conditions that are not standard state, we must use G
rather than Go to predict the direction of the reaction. The
relationship between G and Go is:
Grxn = Gorxn + RT lnQ
(2.9)
Where R is the gas constant (8.314 J.k-1.mol-1)
T the absolute temperature of the reaction
Q is the reaction quotient
G depends on two quantities: Go and RTlnQ.
For a given reaction at temperature T, the value of Go is
fixed but that of RTlnQ is not, because Q varies according
to the composition of the reacting mixture.

At equilibrium, Grxn = 0 and Q = K, where K is the equilibrium
constant.
Thus: 0 = Go + RTlnK or
Go = -RTlnK
(2.10)
Kp is used for gases
Kc for reactions in solution.
Note that, the larger the K is, the more negative Go is.
Go and K are constant for a particular reaction at a given T.
The magnitude of Go indicates the extent to which a chemical
reaction occurs under standard state conditions.
The more negative the Go value, the larger is the value of K
and the more favorable is the formation of products.

Example 1: Calculate the equilibrium constant KP for the
following reaction at 25oC:
2H2O(l) 2H2(g) + O2(g)
According to equation:
Go rxn = [2Gof(H2) + Gof(O2)]- [2Gof(H2O)]=
[(2x0 + 1x0]- [2x(-237.2)] =474.4KJ
lnKp =
G o
474.4 x1000
191.5
RT
8.314 x 298
KP = 7x10-84
This extremely small equilibrium constant is consistent with the
fact that water does not decompose into hydrogen and oxygen
gases at 25oC.

2.8.4. Evaluation of equilibrium constants at different
temperatures
If we know the equilibrium constant, KT1, for a reaction at one
temperature, T1, and also its Ho
We can estimate the equilibrium constant at a second
temperature, T2 using Vant Hoff equation:
K T2
ln
KT
1
H o 1
1
R T1 T2
Ho of reaction is constant in the range of (T1-T2).

If we know Ho for a reaction and K at a given T1=298K, we can
use the Vant Hoff equation to calculate the value of K at any
other T2.

2.9. FACTORS THAT AFFECT CHEMICAL EQUILIBRIUM
Chemical equilibrium represents a balance between

forward and reverse reactions.
Changes in experimental conditions may destroy the
balance and shift the equilibrium position so that more or
less of the desired product is formed.
Variables that can be controlled experimentally are
concentration, pressure, volume and temperature.
We will examine how each of these variables affects a
reacting system at equilibrium.

2.9. FACTORS THAT AFFECT CHEMICAL EQUILIBRIUM
2.9.1. Le Chateliers principle
Le Chateliers principle, states that:
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset.
The word stress here means a change in concentration,
pressure, volume, or temperature that moves a system from
equilibrium state.
2.9.2. Changes in concentration
Consider the following system starting at equilibrium:

When we add more of any reactant or product to the system, the
value of Q changes, the reaction is no longer at equilibrium.
The system shifts in such a way untill a novel equilibrium is
established.
Example:
The equilibrium between undissociated FeSCN2+ and the Fe3+
and SCN- ion is given by:
FeSCN2+(aq)
Fe3+(aq)
+ SCN-(aq)
Red
Pale yellow
Colorless
What happen ? if we add or take out the SCN-

+ if we add some NaSCN to this solution, so the increase in the
concentration of SCN- is applied. To offset this stress, some Fe3+
ions react with the added SCN- ions and the equilibrium shifts
from right to left:
FeSCN2+(aq) Fe3+(aq)
+ SCN-(aq)
Red color of the solution deepens
+ if we added ion (III) nitrate Fe(NO3)3 to the original solution,

the red color would also deepen because the additional Fe3+ ions
would shift the equilibrium from right to left.
+ If we add some oxalic acid (H2C2O4) to the original solution.
Oxalic acid ionizes C2O42, which binds strongly to the Fe3+
ions, so the concentration of Fe3+ decreases in the solution. More
FeSCN2+ units dissociate and the equilibrium shifts from left to
right.
FeSCN2+(aq) Fe3+(aq)
+ SCN-(aq)

These experiments show that increasing the concentrations of
the products (Fe3+ or SCN-) shifts the equilibrium to the left, and
decreasing the concentration of the product (Fe3+) shifts the
equilibrium to the right.
2.9.3. Changes in volume or pressure
Change in pressure is applied only for gaseous system. On the
other hand, concentrations of gases are greatly affected by
changes in pressure.
Look at equation: PV = nRT
n
P RT
V
The term (n/V) is the concentration of the gas and it varies
directly with pressure.

Suppose that the equilibrium system:
N2O4(g) 2NO2(g)
Colorless
Brown
Is in a cylinder.
What happens if we increase the P of the gases by pushing on
the piston at constant T ?
+ The V decreases, the concentration (n/V) of N2O and N2O4
increases. The system is no longer at equilibrium, so we can write:
Qc
NO2 o
[ N 2O4 ]o
+ Because the concentration of NO2 in squared in the equilibrium

constant, so the increase in P resulted in increasing numerator
more than denominator.

+ Thus Qc > Kc and the net reaction will shift to the left until Qc=
Kc.
Conversely, a decrease in P (increase in V) would result in Qc <
Kc and the net reaction would shift to the right untill Qc= Kc.
In general, an increase in P (decrease in V) favors the net
reaction that decreases the total number of moles of gases (the
reverse reaction, in this case) and a decrease in P (increase in V)
favors the net reation that increases the total number of moles of
gases.
For reactions in which there is no change in the number of
moles of gases, a pressure (or volume) change has no effect on the
position of equilibrium.

2.9.4. Change in temperature
A change in C, P or V may alter the equilibrium position, but it
does not change the value of the equilibrium constant.
Only a change in T can alter the equilibrium constant.
The formation of NO2 from N2O4 is an endothermic process:
N2O4 (g) 2NO2(g) Ho= 58KJ
And the reverse reaction is an exothermic:
2NO2(g) N2O4 (g) Ho= -58KJ
What happen if the equilibrium system: N2O4 (g) 2NO2(g) is
+ heated at constant V ? Since endothermic reaction absorb heat
from the surroundings, heating favors the dissociation of N2O4 into
NO2.
+ Cooling favors the exothermic reaction (the formation of N 2O4)
the system turns pale brown.

In summary, a temperature increase favors an

endothermic reaction and a temperature decrease favors
an exothermic reaction.
Chapter 3: Solution
3.1. Concentration units
Concentration is the amount of solute present in a given amount
of solution.
There are several concentration units such as percent by mass,
mole fraction, molarity and molality.
* Percent by mass
The percent by mass (also called percent by weight or weight
percent) is the ratio of the mass of a solute to the mass of the
solution, multiplied by 100 percent.
The percent by mass has no units because it is a ratio of two
similar quantities.
* Molarity (M)
Molarity is defined as the number of moles of solutes in 1 liter of
solution.
* Molality:
Molality is the number of moles of solute dissolved in 1kg of
solvent.
Chapter 3: Solution
3.2. PRINCIPLES OF SOLUBILITY
3.2.1.Type of solutions
Solution is a homogeneous mixture of two or more
substances.
Solutions can be characterized by their capacity to dissolve
a solute.
* A saturated solution contains the maximum amount of a
solute that will dissolve in a given solvent, at a specific
temperature.
* An unsaturated solution contains less solute than it has the
capacity to dissolve.
* A supersaturated solution, contains more solute than is
present in a saturated solution.
Supersaturated solutions are not very stable. In time, some of
the solute will come out of a supersaturated solution as
crystals.
Chapter 3: Solution
3.2.2. A view of the solution process

we can imagine the solution process taking place
in three distinct steps.
Step 1 is the separation of solvent molecules
Step 2 entails the separation of solute
molecules. These steps require energy input to
break
attractive
intermolecular
forces;
therefore, they are endothermic.
Step 3 the solvent and solute mix. This process
can be exothermic.
Hsoln. = H1 + H2 + H3
Chapter 3: Solution
3.2.3. The effect of temperature on solubility
Temperature affects the solubility of most substances.
1. In most but certainly not all cases, the solubility of
a solid substance increases with temper. However,
there is no clear correlation between the sign of
Hsoln and the variation of solubility with temper.
For example, the solution process of CaCl 2 is
exothermic, and that of NH4NO3 is endothermic.
But the solubility of both compounds increases
with increasing temperature.
2 The solubility of gases in water usually decreases
with increasing temper.
Chapter 3: Solution
3.2.4. The effect of pressure on the solubility of gases
For all practically purposes, external pressure has
no influence on the solubilities of liquid and solids,
but it does greatly affect the solubility of gases.
The quantitative relationship between gas solubility
and pressure is given by Henrys law
which states that the solubility of a gas in a liquid is
proportional to the pressure of the gas over the
solution
c = kP
Chapter 3: Solution
3.2.4. The effect of pressure on the solubility of gases
Here, c is the molar concentration (mol/l) of the
dissolved gas;
P is the pressure (in atm) of the gas over the
solution;
For a given gas, k is a constant that depends only on
temper. The constant k has the units mol/L.atm.
The limitation of Henrys law: apply for gases
having low solubility and no interaction with
solvent and low pressure.
Chapter 3: Solution
3.2.5. Colligative properties of nonelectrolyte
solutions
The colligative properties are vapor-pressure
lowering, boiling-point elevation, freezing-point
depression.
For our discussion of colligative properties of
nonelectrolyte solutions it is important to keep in
mind that we are talking about relatively dilute
solutions, that is, solutions whose concentrations are
0.2M.
Chapter 3: Solution
solutions
Vapor- pressure lowering
If a solution containing a nonvolatile solute, the vapor
pressure of its solution is always less than that of the
pure solvent.
Psoln < Psovl
The boiling-point elevation
The boiling-point elevation of a solution containing
nonvolatile solute is defined as the boiling point of the
solution (Tb minus the boiling point of the pure solvent
(Tob) Tb = Tb - Tob
Chapter 3: Solution
solutions
Freezing point depression
The freezing point depression of a solution
containing nonvolatile solute is defined as the
freezing point of the solvent (Tof) minus the freezing
point of the solution (Tf)
Tf = Tof - Tf
Chapter 3: Solution
3.2.6 Colligative properties of electrolyte solutions
In solution, electrolytes dissociate into ions, and so

one unit of an electrolyte compound separates into
two or more particles, when it dissolves.
For example: each unit of NaCl dissociates into two
ions Na+ and Cl-.
Thus, the colligative properties of a 0.1M solution of
NaCl should be twice as great as those of a 0.1 M
solution containing a nonelectrolyte, such as
sucrose.
Chapter 3: Solution
3.2.5. Colligative properties of electrolyte solutions
Experimentally showed that the experimental values of
vapor- pressure lowering, boiling point elevation and
freezing point depression of electrolyte solutions are
always more than that of the theoretical, so that:
P= iP
Tb= iTb
Tf= iTf
The variable i is the Vant Hoff factor, which is defined as
Actual number of particles in solution after dissociation
i = --------------------------------------------------------------------Number of formula units initially dissolved in soln
Thus i should be 1 for all nonelectrolytes and more than 1 for electrolytes
Chapter 3: Solution
There are two types of electrolytes
Strong electrolytes are substances that dissociate
completely into ions in solution
such as strong acid: HNO3, H2SO4, HCl, etc.
strong base: NaOH, KOH, Ca(OH)2
soluble salts: NaCl, Na2SO4, NaCH3COO,etc
Weak electrolytes are substances that dissociate
partially in solution. At equilibrium nondissociated
molecules of weak electrolytes exist with their ions
such as weak acid: H2S, HNO2, H3PO4, etc
weak base: NH3
poorly electrolytes: AgCl, CaSO4
Chapter 3: Solution
3.3. BRONSTED ACID-BASE THEORY
3.3.1. Concept of acid- base by Bronsted
Bronsted acid is a substance which is capable of donating a
proton and a Bronsted base as a substance that can accept a
proton.
Every Bronsted acid has a conjugate base, and every
Bronsted base has a conjugate acid. For example, the chloride
ion (Cl-) is the conjugate base formed from the acid HCl, and
H2O is the conjugate base of the acid H3O+ (hydronium ion).
HCl + H2O = Cl+ H3O+ (1)
Acid1
Base1
Base2
Acid2
Similarly, the ionization of acetic acid can be represented as
CH3COOH + H2O CH3COO- + H3O+
Acid1
Base1
Base2
Acid2
Chapter 3: Solution
The Bronsted definition also allows us to classify
ammonia as a base because of its ability to accept
a proton
NH3 + H2O NH4+ + OHbz1
ax2
ax1
bz2
3.3.2.The acid-base properties of water

Water is a unique solvent.
Water has ability to act either as an acid and as a
base.
Water is a very weak electrolyte and therefore a
poor conductor of electricity, but it does
undergoes ionization to a small extent:
Chapter 3: Solution
H2O + H2O OH- + H3O+ (autoionization)
ax1
bz2
bz1 ax2
In the study of acid-base reactions in aqueous
solutions, the hydrogen ion concentation is key,
because it indicates the acidity or basicity of the
solution.
Expressing the proton as H+ or H3O+, we can write
the equilibrium constant of the autoionization of
water as:
H OH
KC
H 2 O
Chapter 3: Solution
Since a very small fraction of water are ionized, the
concentration of water [H2O] remains unchanged.
Therefore:
Kc[H2O]= [H+][H3O+] = const = Kw
(3.2)
The equilibrium constant Kw is called the ionproduct constant, which is the product of the molar
concentrations of H+ and OH- at a particular
temperature.
Chapter 3: Solution
In pure water at 25oC, the concentrations of H+ and
OH- ions are equal and found to be [H+] = [OH-] =
10-7M.
Thus, from equation (3.2) at 25oC:
Kw = [H+][OH-] = 10-14
- When [H+] = [OH-] = 10-7M, the aqueous solution
is said to be neutral
- In an acidic solution (there is an excess of H+ ions)
- In a basic solution (there is an excess of OH- ions)
Chapter 3: Solution
3.3.3. pH- a measure of acidity
Because the concentrations of H+ and OH- ions in aqueous
are very small numbers
Soren Sorensen in 1909 proposed a more practical measure
called pH.
The pH of a solution is defined as the negative logarithm of
the hydrogen ion concentration (in mol/l)
pH= - lg[H+]
Acidic and basic solutions at 25oC can be distinguished by
their pH values as follows:
Acidic solutions: [H+] > 10-7 M, pH < 7
Basic solutions: [H+] < 10-7 M, pH > 7
Neutral solutions: [H+] = 10-7 M, pH =7
Chapter 3: Solution
3.3.4. Strength of acids and bases
1. Strong acids are strong electrolytes which dissociate
completely in water into ions.
Most of the strong acids are inorganic acids: hydrochloric
acid HCl, nitric acid HNO3, perchloric acid HClO4 and
sulfuric acid H2SO4.
HCl H+ + Cl2. Strong bases are all strong electrolytes that ionize
completely in water.
Hydroxides of alkali metals and alkaline earth metals are
strong bases. All alkali metals hydroxides are soluble, the
alkaline earth hydroxides Be(OH)2, Mg(OH)2 are insoluble;
Ca(OH)2 and Sr(OH)2 are slightly soluble.
NaOH Na+ + OH-
Chapter 3: Solution
3. Most weak acids ionize only to a limited extent in
water. At equilibrium, aqueous solutions of weak
acids contain
a mixture of nonionized acid
molecules, H3O+ ions and the conjugate base.
Examp. of weak acids HF, CH3COOH and
ammonium ion NH4+.
CH3COOH CH3COO- + H+
4. Weak bases are weak electrolytes. Ammonia is a
weak base. It ionizes to a very limited extent in
water:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
Chapter 3: Solution
Conjugate acid-base pairs have the following properties:
- If an acid is strong, its conjugate base has no measurable
strength. Such as the ion Cl-, which is the conjugate base of
the strong acid HCl, is an extremely weak base, so HCl reacts
with water completely to form H3O+ and ClHCl + H2O Cl+ H3O+
- If an acid is a weak, it can react with water at a small extent
to form H3O+ and its conjugate base.
HF + H2O
F + H3O+
-If a base is strong, its conjugate acid has no strength
(extremely weak acid), so the conjugate of strong base can
react with water
- CH3COO- + H2O
CH3COOH + OH- A weak base reacts with water at very small extent to
produce OH- and its conjugate acid, its conjugate base can
react with water.
Chapter 3: Solution
3.3.5. Weak acids and acid ionization constant
The vast majority of acids are weak acids. Consider an
ionization of a weak acid, HA:
HA + H2O A- + H3O+
The equilibrium expression for this ionization is
H O . A
Ka
HA
= constant at T= constant
Ka is called the acid ionization constant. At a given T, the

strength of the acid HA is measured by the magnitued of
Ka. The larger the Ka, the stronger the acid- that is, the
greater the concentration of H+.
Chapter 3: Solution
3.3.6. Weak bases and base ionization constant
B + H2O BH+ + OHThe ionization of weak base is treated in the same way
as the ionization of weak acids.
The equilibrium constant is given by:
BH . OH
Kb
= constant at T= constant
Kb is the base ionization constant, which is constant

at a particular temperature.
Chapter 3: Solution
3.3.7. The relationship between the ionization constants of

acids and their conjugate bases
An important relationship between the ionization constant of
an acid and the ionization constant of its conjugate base can
be derived as follows
A + H2O B + H3O+
Ka
B + H2O A + OHKb
B.H 3O
Ka
A
A .OH
Kb
B
B.H 3O A .OH
K a .K b
.
H 3O . OH K H O 10 14
A
B
2
For any conjugate acid-base pair it is true that Ka.Kb = 10-14

at 250C
Chapter 3: Solution
3.3.7. The relationship between the ionization constants of

acids and their conjugate bases
An important relationship between the ionization constant of
an acid and the ionization constant of its conjugate base can
be derived as follows
A + H2O B + H3O+
Ka
B + H2O A + OHKb
B.H 3O
Ka
A
A .OH
Kb
B
B.H 3O A .OH
K a .K b
.
H 3O . OH K H O 10 14
A
B
2
For any conjugate acid-base pair it is true that Ka.Kb = 10-14

at 250C
Chapter 3: Solution
Thus, for any conjugate acid-base:
Ka = KW/Kb
and
Kb = KW/Ka
Conclusion: the stronger the acid (the larger Ka), the

weaker its conjugate base (the smaller Kb) and vice
versa.
Example: if we know Ka(CH3COOH) = 1.8x10-5
Kb(CH3COO-) = 10-14/1.8x10-5 = 5.6x10-10
Chapter 3: Solution
3.3.8. Calculate pH of
(monoprotic acid)
weak acid solutions
Calculate pH of weak acid HA with initial concentration

Ca
HA + H2O A2H2O
+ H3O+ Ka
H3O+ + OH-
(1)
(2)
H 3O OH K H 2O
H 3O . A
K a
HA
H O A OH
3
HA Ca A
Solve the cubic equation, find [H3O+] and pH
Chapter 3: Solution
* Approximation method (5% error)
1. If Ca.Ka 10-12
and If 0.1 < Ca/Ka < 100, so the ionization of H2O can
not be considered
We consider the ionization of weak acid only
HA + H2O A- + H3O+
Initial
Ca
0
0
Equilibrium Ca- x
x
x
Ka
x2
Ca x
Solving the quadratic equation,

find x pH
Chapter 3: Solution
2. If Ca.Ka 10-12
and Ca/Ka > 100. Very weak acid, so x << Ca, consider Ca-x
Ca
x2
Ka
Ca
x K a .C a calculate pH
Chapter 3: Solution
Note:
1.
To calculate pH of strong acids (for example HCl),

you do not need solve through the acid ionization
constant.
If strong acid is not too much dilute, Ca > 3.17x10-7
M, then [H3O+] due to autoionization of water can
be ignored, thus [H3O+] = Ca and pH = -lgCa
If strong acid is too much dilute, Ca < 3.17x10-7 M,
then you should consider [H3O+] of autoionization
of H2O. To calculate pH you have to rely on the
neutralization of charges and the ion-product
constant of H2O:
Chapter 3: Solution
H 3O . OH K H 2O
H 3O OH Cl OH C a
K H 2O
H O H O C
H 3O
C H O K
H 2O
Solving the quadratic equation you can find

[H3O+]
Chapter 3: Solution
2. To calculate pH of the solutions of diprotic and polyprotic

acids.
+ These acids may yield more than one hydrogen ion.
+ These acids ionizes in a stepwise manner, that means, they
lose H+ ions step by step and an ionization constant
expression can be written for each ionization step. For
carbonic acid H2CO3, we write:
H2CO3(aq) + H2O HCO3-(aq) + H3O+(aq) Ka1 = 4.1
x10-7
HCO3-(aq) + H2O CO32-(aq) + H3O+(aq)
Ka2 = 4.8
x10-11
+For a given acid, the 1st ionization constant is much larger
than the 2nd ionization constant. Thus, we can consider only
the 1st step take place, ignore the 2nd step. Calculate pH of
Chapter 3: Solution
Example 1: Calculate pH of 0.1M CH3COOH, knowing

Ka = 1.8x10-5
Due to Ca.Ka = 0.1x1.8.10-5 = 10-6 > 10-12, ionization of
H2O can be ignored
Ca
10 1
100
5
K a 1.8 x10
[H3O+] < < Ca, so Ca- x Ca
H O
K a .C a 1.8 x10 5 x10 1
pH lg 1.8 x10 6 2.87
Chapter 3: Solution
3.3.9. Calculate pH of weak bases

Consider the ionization equilibrium of weak base B in
solution (A is the conjugate acid)
B + H2O A + OH2H2O H3O+ + OHAs in the case of weak acids, to calculate pH we have to
approach to the method of approximation:
* If Cb.Kb 10-12
And 0.1 C b 100
Kb
Chapter 3: Solution
We consider the following equilibrium:

B + H2O A + OH[OH-] = x
Initial
Cb
0
0
Equilibrium Cb-x
x
x
x2
Kb
Cb x
Solving the quadratic equation, find [OH-]
Chapter 3: Solution
* If Cb.Kb 10-12
Cb
100
Kb
very weak base, so x<< Cb Cb - x Cb

Cb .K H O
x = [OH ] Cb .K b
2
Ka
Chapter 3: Solution
Note:
1. If base is not too much dilute, Cb > 3.17x10-7M, then we
ignore OH- by ionization of H2O,
thus [OH-] = Cb p(OH) = - lgCb
pH + p(OH) = 14 pH= 14 + lgCb
2. If base is much dilute, Cb < 3.17x10-7M, then we have to
consider [OH-] by ionization of H2O. To calculate [OH], we need rely on the neutralization of charges and the
ionization product constant of H2O. That means we
have to solve the equation system
H
O
.
OH
K H 2O
3
OH
H
O
Na
H
O
Cb
3
3
Chapter 3: Solution
K H 2O
OH OH C
pH
OH C b . OH K H 2O 0
Chapter 3: Solution
3.3.10. Hydrolysis of salts

1. Concept of hydrolysis
Salt hydrolysis is a reaction of an anion or cation of salt or
both, with water, resulted in changing in pH of a solution.
For instance: Al3+ is a cation of weak base Al(OH)3 will
undergo hydrolysis:
Al3+.H2O + H2O
Al2+OH + H3O+
Al2+OH + H2O
Al(OH)2+ + H3O+
Al(OH)2+.H2O + H2O Al(OH)3 + H3O+
Hydrolysis is a reversible reaction
Hydrolysis occurs by a stepwise manner and the hydrolysis
constant of the 1st step is always much stronger than that of
the following steps
If the solution is very dilute, so the hydrolysis reaction can
occur completely
Chapter 3: Solution
2. Salts that produce neutral solutions:

2.1. Salts containing an alkali metal ion or alkaline earth
metal ion and the conjugate base of a strong acid (for exampe
Cl-, Br- and NO3-) do not undergo hydrolysis, and their
solutions are assumed to be neutral.
For instance, when NaNO3 (salt derives from strong base
and strong acid), dissolves in water, it dissociates completely
as follows:
NaNO3 Na+(aq) + NO3-(aq)
The hydrated ion Na+ is the conjugate acid of strong base
NaOH which does not donate H+ ion.
The NO3- ion is the conjugate base of strong acid HNO3, and
it has no affinity for H+ ion. Consequently, a solution
containing Na+ and NO3- ions is neutral.
Chapter 3: Solution
2.2. Salts that produce basic solutions

The solution of a salt derived from a strong base and a weak
acid is basic. For example, the dissociation of sodium acetate
CH3COONa in water given by:
CH3COONa Na+(aq) + CH3COO-(aq)
- The hydrated Na+ ion has no acidic properties.
- The acetate ion CH3COO-, is the conjugate base of the weak
acid CH3COOH and therefore has an affinity for H+ ion. The
hydrolysis reaction of acetate ion is given by:
CH3COO-(aq) + H2O
CH3COOH(aq)+ OH-(aq)
Kb
(CH3COO-)
_
CH
COO
CH 3COOH OH
3
hydrolyzed
10
%hydrolysis
x100%
Kb
5
.
6
x
10
CH 3COO initial
CH 3COO
Na2S, K2CO3, KNO2....
Chapter 3: Solution
2.3. Salts that produce acidic solutions

A salt derived from a strong acid such as HCl and a weak
base such as NH3 dissolves in water, the solution becomes
acidic. For example, consider the process:
NH4Cl NH4+(aq) + Cl-(aq)
The Cl- ion, being the conjugate base of a strong acid, has no
affinity for H+ and no tendency to hydrolyze. The NH 4+ is
the conjugate acid of the weak base NH3 and ionizes as
follows
NH4+(aq)+ H2O
NH3(aq) + H3O+(aq)
Ka
(NH4+)
14
Since H+ ions are
decreases.
The
NHproduced,
KW the 10pH
10
3 H
Ka
5.6 x10
5
equilibrium constant
(or
ionization
constant)
NH 4 K b 1.8x10 for this process
is given
NH NOby:
, (NH ) SO
4
42
Chapter 3: Solution
2.4. Salts in which both the cation and the anion

hydrolyze
Salts derived from a weak acid and a weak base, both
the cation and the anion hydrolyze.
However, whether a solution containing such a salt is
acidic, basic or neutral depends on the relative strengths
of the weak acid and the weak base.
There are three cases
Chapter 3: Solution
Case 1: If Kb (of anion of weak acid) > Ka (of cation of weak

base), then the solution must be basic because the anion will
hydrolyze to a greater extent than the cation. At equilibrium,
there will be more OH- ions than H+ ions
Case 2: If Kb (of anion of weak acid) < Ka ( of cation of weak
base), the solution will be acidic because cation hydrolysis
will be more extensive than anion hydrolysis
Case 3: If Kb (of anion of weak acid) Ka (of cation of weak
base), then solution will be nearly neutral.
Examples
(NH4)2S NH4+ + S2NH4+ + H2O NH3 + H3O+
(Ka(NH4+)) = 5.6x1010
S2- + H2O HS- + OH(Kb(S2-)) = 105
Chapter 3: Solution
NH4CH3COO NH4+ + CH3COONH + + H O NH + H O+
10)
(Ka(NH4+)) = 5.6x10-
CH3COO- + H2O CH3COOH + OH(Kb(CH3COO-) = 5.7

x10-10)
Ka(NH4+) Kb(CH3COO-), therefore pH =7
Note: Calculate pH of salts as calculate pH of weak

monoprotic acid or weak base.
Example: Calculate pH of 0.2M K2CO3, knowing Ka2
(H2CO3) =5.6x10-11
K2CO3
2K+ + CO32CO32- + HOH HCO3- + OHKb(CO32-)
CO32- is the conjugate base of acid HCO3-: HCO3/CO32Ka(HCO3-).Kb(CO32-)= 10-14 and Ka(HCO3-)=Ka2
-11
Chapter 3: Solution
14
210
Kb(CO3 ) =
K
a
10 14
1.78 x10 4
11
5.6 x10
We consider the approximation method

Kb.Cb = 0.2x1.78.10-4 > 10-12 ignore the ionization of H2O
Cb
0,2
100
4
Kb
1,78.10
OH
K b .C b 1.78 x10 4 x0.2 pH 14 lg 1.78 x10 4 x0.2 11.7

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Part II: Fundamental laws of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Part II: Fundamental laws of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Sign of heat and work

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

1.3.3. Enthalpy (heat) of formation

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

In a contrast with enthalpy of formation is enthalpy of

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Example: Calculate Ho 298 for the reaction

Ho298,react.= Ho298,f(CO2g) + 2.Ho298,f(H2Ol)Ho298,f(CH4g)= -890,34KJ.mol-1

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

1.5.2. Enthalpy of reaction

Chapter 1: Thermodynamics of chemical

A schematic representation of relationship

Chapter 1: Thermodynamics of chemical

N2(g) + 3H2(g) 2NH3(g)

EN-H = -391 KJ.mol-1; ENN = -945KJ.mol-1; EH-H = -436

Using the bond energy form of Hesss Law

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

We come to the following conclusion: Exothermicity

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

It is possible to determine the absolute

Chapter 1: Thermodynamics of chemical

Entropy is a state function.

Chapter 1: Thermodynamics of chemical

1.6.3. Statement of the 2nd Law of thermodynamics

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

1.7. GIBBS FREE ENERGY

1.7.1. Establish the spontaneity criterion of reactions

Chapter 1: Thermodynamics of chemical

1.7. GIBBS FREE ENERGY

For convenience, we can change the above equation,

Chapter 1: Thermodynamics of chemical

1.7. GIBBS FREE ENERGY

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical

Chapter 1: Thermodynamics of chemical