Thermodynamics of Solutions

and Electrochemistry

22306 Physical Chemistry I

Text Book: Atkins, Physical Chemistry

 Thermodynamics of Solutions &
Electrochemistry
• Physical Transformations of Pure
Substances
• Properties of Simple Mixtures
• Chemical Equilibrium
• Equilibrium Electrochemistry
 Physical Transformation of Pure
Substances

• Gibbs Energy and Chemical Potential

• Phase Diagrams
• Phase Stability and Phase Transitions
Gibbs Energy& Chemical Potential

*Gibbs Energy: G = H - T S
Enthalpy Entropy

*Chemical Potential: m = (G / n)p,T

amount of substance (in moles)

m = ( (nGm) / n )p,T = Gm
Molar Gibbs energy
Phase Diagrams

Tc
 Phase Stability & Transitions

At equilibrium, the chemical potential of a substance

is the same throughout the sample, regardless of how
many phases are present.

*Chemical potentials:

m1 = m2
*Justification
Consider a system in which the chemical
potential of a substance is m1 at a location
and m2 at another location.

When dn of the substance is transferred from

one location to the other, the change of Gibbs
energy:
dG = (m2-m1) dn

If m1 > m2
dG < 0
Thus, a spontaneous change occur until
m1 = m2
The dependence of stability on the conditions

Chemical potentials:
Solid m(s)
Liquid m(l)
Gas m(g)
The temperature dependence of phase stability
*A Thermodynamics Relationship:
( G / T )p = - S

Since m = Gm
*( m / T )p = - Sm< 0

(1) As temperature is raised, the chemical potential of a pure

substance decreases.
(2) The slope of m versus T is steeper for gases than for liquids,
and steeper for a liquid than the solid.
(3) The steep negative slope of m(l) results in its falling below
m(s) when the temperature is high enough, and liquid becomes
the stable phase: the solid melts.
(4) m(l) plunges steeply downwards as T is raised, and there
comes a temperature at which it lies lowest: the liquid vaporizes.
The response of melting to applied pressure
*A Thermodynamics Relationship:
( G / p )T = V

Since m = Gm
*( m / p )T = Vm> 0

(1) As pressure is raised, chemical potential of a pure substance

increases.

(2) In most cases Vm(l) > Vm(s), an increase in pressure increases

m(l) more than m(s), and raises the melting temperature.

(3) Vm(l) < Vm(s), an increase in pressure increases m(s) more

than m(l), and lowers the melting temperature.
*(a) Vm(l) > Vm(s) m

High pressure
Low pressure

Tf Tf ’ T

*(b) Vm(l) < Vm(s) m

High pressure

Low pressure

Tf ’ Tf T
The effect of applied pressure on vapour pressure
P

p
Piston permeable to vapour

Relation between vapour pressure and applied pressure on liquid:

p = p* eVmP/RT
where
p vapour pressure
p* vapour pressure w/o additional pressure
P additional pressure
Vm molar volume
Justification
At equilibrium: m(l) = m(g)
dm(l) = dm(g)
at constant temperature,
dm(l) = Vm(l) dP
dm(g) = Vm(g) dp
assume vapour is ideal,
Vm(g) = RT / p
dm(g) = RT dp / p = Vm(l) dP
integration:
RT dp / p =  Vm(l) dP
Finally,
RT ln(p/p*) = Vm(l) P
 The location of phase boundaries

Phase boundary:
the pressures and temperatures at which two
phases (a & b) can coexist

*ma(p,T) = mb(p,T)
*dma(p,T) = dmb(p,T)
The slopes of the phase boundaries

dm = Vmdp - SmdT
Va,mdp - Sa,mdT = Vb,mdp - Sb,mdT

Clapeyron Equation:
dp / dT = Sm / Vm

Sm = Sb,m - Sa,m

Vm= Vb,m - Va,m
The solid-liquid boundary
Thermodynamics Relationship:
H = T S

Melting (fusion) is accompanied by a molar enthalpy change

fusH at a fixed temperature T.

dp / dT = fusH / TfusV

(1) fusH > 0 (except 3He).

(2) fusV is usually positive, and thus dp / dT > 0
(3) fusH and fusV barely change over temperature & pressure

p = p* + (fusH / fusV) ln(T/T*)

p = p* + (fusH / T*fusV) (T-T*)
The liquid-vapour boundary

Vaporization is accompanied by a molar enthalpy change vapH at

a fixed temperature T.

dp / dT = vapH / TvapV

(1) vapH > 0

(2) vapV is large and positive, dp / dT > 0 but less than melting
(3) Clausius-Clapeyron equation:

d ln p / dT = vapH / RT2
The solid-vapour boundary

Sublimation is accompanied by a molar enthalpy change subH at

a fixed temperature T.

dp / dT = subH / TsubV

(1) subH > 0

(2) subV is large and positive, dp / dT > 0
(3) Clausius-Clapeyron equation:

d ln p / dT = subH / RT2
The Ehrenfest classification of phase transitions

First-order transition: a transition for which the first

derivative of chemical potential m with respect to T is
discontinuous (eg. Fusion, vaporization)
First-order transition is also characterized by the infinite heat
capacity at the transition temperature
(mb / T )p - (ma / T )p = - Sa,m+ Sb,m = -S = -H / T

Second-order transition: a transition for which the first

derivative of chemical potential m with respect to T is
continuous but the second derivative is discontinuous
(eg. Conductor-superconductor)
 Properties of Simple Mixtures

• Thermodynamic Description of Mixtures

• Properties of Solutions
• Activities
 System

Binary Mixtures (two components A & B)

that do not react together and have weak or
no interaction among the constituents.
 The thermodynamic description of
mixtures
• Partial molar properties
• The thermodynamics of mixing
• The chemical potentials of liquids
 Partial molar quantities

14 cm3
1 mole water 18 cm3
water &
ethanol water
25oC
The quantity 14 cm3/mol is the partial molar volume of water
in pure ethanol
Partial molar volume
Partial molar volume of a substance J in a mixture is the change
in volume on the addition of 1 mol J to a large excess of mixture

The partial molar volume VJ of substance J at some composition:

*VJ = V





nJ  p,T,n’



nJ is the amount (the number of moles) of J

n’ the amounts of all other substances
VJ depends on the composition of the mixture
Total volume V of the mixture (A & B)

*V = nAVA + nBVB
Justification V = nAVA + nBVB

Consider a very large sample of the mixture of the same composition.

(1) when nA of A is added, the composition is virtually unchanged,

the volume increases by nAVA

(2) when nB of B is added, the composition is virtually unchanged,

the volume increases by nBVB

(3) after nA of A and nB of B are added, total volume increases by

nAVA + nBVB

(4) Now scoop out of the enlarged volume a sample containing

nA of A and nB of B. Its volume V is nAVA + nBVB
Partial molar Gibbs energies
Partial molar Gibbs energy is simply the chemical potential

The chemical potential mJ of substance J at some composition:

*mJ = G





nJ  p,T,n’



nJ is the amount (the number of moles) of J

n’ the amounts of all other substances

Total Gibbs energy G of the mixture (A & B)

*G = nA mA + nBmB
The Gibbs-Duhem equation

 nJ dmJ = 0
J

The change of Gibbs energy G of the mixture (A & B)

dG = mAdnA + mBdnB + nAdmA + nBdmB

At constant pressure and temperature,

dG = mAdnA + mBdnB

nAdmA + nBdmB = 0
the chemical potentials of a mixture cannot change independently:
in a binary mixture, if one increases the other must decrease.
The thermodynamics of mixing

Gas A
Gas A & B

Gas B
The Gibbs energy of mixing

The Gibbs energy of mixing gases A & B mixG

mixG = nART ln (pA / p) + nBRT ln (pB / p)

mixG = nRT ( xA ln xA + xB ln xB ) < 0

xJ = pJ / p

For a perfect gas,

*m = m0 + RT ln ( p / p0)
where m0 and p0 are the standard chemical potential and pressure
Justification
Consider two perfect gases A & B with the amounts nA & nB at
pressure p and temperature T before mixing
Gi = nA mA + nBmB
= nA {mA + RT ln (p / p)} + nB {mB + RT ln (p / p)}

After mixing,
Gf = nA mA + nBmB
= nA {mA + RT ln (pA / p)} + nB {mB + RT ln (pB / p)}

The difference Gf - Gi, the Gibbs energy of mixing mixG

mixG = Gf - Gi
= nART ln (pA / p) + nBRT ln (pB / p)
Other thermodynamic mixing functions

The entropy of mixing gases A & B mixS

mixS = - (  mixG /  T )
= - nR ( xA ln xA + xB ln xB ) > 0

The enthalpy of mixing gases A & B mixH

mixH = mixG + T mixS = 0

 The chemical potentials of liquids

Composition  ? Chemical Potential

Chemical potential of a substance in vapor is equal to

its chemical potential in liquid
Ideal solutions

Chemical potential of pure liquid

mA*(l) = mA*(g) = mA0 + RT ln (pA* / p0)
[ * represents the pure liquid, eg. pA* is the vapor
pressure of pure liquid A; l represents liquid, g for
gas]

Chemical potential of A in a solution

mA(l) = mA(g) = mA0 + RT ln (pA / p0)
[ pA is the vapor pressure of A ]

*mA(l) = mA*(l) + RT ln (pA / pA*)

important relation
 *Raoult’s Law: Vapor pressure of pure A

pA = xA pA*
xA = nA / n mole fraction
Vapor pressure of A in mixture
Toal mole number of solution
Mole number of A

Ideal Solutions: Mixtures that obey the Raoult’s law

throughout the composition range (xA: 01)

Some solutions depart siginificantly from the Raoult’s law.

Even in these case the law is obey increasingly closely for
the component in excess (the solvent) as it approaches purity.
Chemical potential of A in a solution
*mA(l) = mA*(l) + RT ln xA
Justification

Rate of A leaving the surface is proportional to the number of A at

the surface, which is proportional to the mole fraction of A
rate of vaporization = k xA (k is a proportionality constant)

Rate of A returning to the surface is proportional to the vapor con-

centration of A, which is proportional to the partial pressure of A
rate of condensation = k’ pA (k’ is a proportionality constant)
At equilibrium, two rates are equal: k xA = k’ pA
pA = xA k / k’

for pure A, xA = 1, pA* = k / k’

Ideal-dilute solutions

Real solutions may not obey Raoult’s law. English chemist Henry
found that at low concentrations the vapor pressure of the solute
is proportional to its mole fraction

*Henry’s Law:
pB = xB KB
xB is the mole fraction of the solute
KB is constant but not partial pressure of B

Ideal-dilute solutions: Mixtures for which (a) the solute obeys

Henry’s law but not Raoult’s law; and (b) the solvent obeys
Raoult’s law.
 The Properties of Solutions

Ideal liquid A

Ideal liquid
A+B
Ideal liquid B

• Liquid mixtures
• Colligative properties
 Liquid mixtures

Before the mixing: Gi = nA mA*(l) + nB mB*(l)

After the mixing:

Gf = nA { mA*(l) + RT ln xA } + nB { mB*(l) + RT ln xB }

The Gibbs energy of mixing:

mixG = n RT { xA ln xA + xB ln xB } < 0
n = nA + nB

(1) driving force for mixing is the increasing entropy

(2) the enthalpy of mixing is zero
Real solutions:
(1) A-A, A-B & B-B interactions are all different
(2) Excess functions
GE = mixG(actual) - mixG(ideal)
SE = mixS(actual) - mixS(ideal)

Deviations of excess functions from zero indicate

the extent to which the solutions are non-ideal

mixG > 0, immiscible; mixG < 0, miscible;

 Colligative properties

solvent solute

Colligative properties: properties of solutions depend only

on the number of solute particles

Assumptions:
(1) The solute is not volatile, so it does not contribute
to the vapor;
(2) The solute does not dissolve in the solid solvent.
The common features of colligative properties

*Reduction of the chemical potential of liquid solvent in the

presence of solute;
No direct influence of the solute on the chemical potential of
the solvent vapor and the solid solvent (because the non-volatile,
insoluble solute does not appear in either the vapor or the solid);

*Reduction of the chemical potential of the solvent leads to a

higher boiling temperature and a lower melting temperature.
 m
*Justification solid pure liquid
solution

vapour

Tf ’ Tf Tb Tb’
Chemical potential   Entropy 

Entropy   weaker tendency to form gas

 higher boiling temperature

Entropy   Randomness   weaker tendency to freeze

 freezing temperature 
The elevation of boiling point
Under 1 atm pressure, mA*(g) = mA*(l) + RT ln xA

The increase of the boiling temperature T*  T* +  T

T = (RT*2 / vapH) xB

(A & B being the solvent and solute, respectively; * represents

pure liquid)

A(g) mA*(g,p)

A(l) + B mA(l)
Justification
mA*(g) = mA*(l) + RT ln xA
ln ( 1- xB ) = ( mA*(g) - mA*(l) ) / RT = vapG / RT
where vapG is the molar Gibbs energy of vaporization of pure A,
xA + xB = 1 has been used.
vapG = vapH - T vapS
ln ( 1- xB ) = vapH / RT - vapS / R
when xB = 0, the boiling point of the pure liquid A, T*:
ln 1 = vapH / RT* - vapS / R
ln ( 1- xB ) = vapH / R ( 1 / T - 1 / T* )
Usually xB << 1,
xB = vapH / R ( 1 / T* - 1 / T )
For T  T*,
1 / T* - 1 / T = ( T - T* ) / TT*  T / T*2
The increase of the boiling temperature
T = (RT*2 / vapH) xB
The depression of freezing point
Under 1 atm pressure, mA*(s) = mA*(l) + RT ln xA

The decrease of the freezing temperature T*  T* -  T

T = (RT*2 / fusH) xB

(A & B being the solvent and solute, respectively)

Solubility
Under 1 atm pressure, mB*(s) = mB*(l) + RT ln xB

ln xB = ( mB*(s) - mB*(l) ) / RT
= - fusG / RT
= - (fusH / RT) + fusS / R

If the enthalpy and entropy of melting are constant,

ln xB = - (fusH / R) ( 1 / T - 1 / T*)

Melting or freezing temperature

At T*, fusG = 0  fusG / RT* = 0  (fusH - T*S) / RT* = 0

Osmosis

Osmosis: the passage of a pure solvent into a solution separated

from it by a semipermeable membrane, a memberane permeable
to the solvent but not to the solute
Osmosis pressure : pressure that must be applied to the solution
to stop the influx of solvent
semipermeable
membrane
p p+

mA*(p) mA(p+)

Van’t Hoff equation

*For dilute solution,  V = nB RT
Justification
At equilibrium, mA*(p) = mA(p+)
In the presence of solute B, mA(p+) = mA*(p+) + RT ln xA
At constant temperature, mA*(p+) = mA*(p) +  pp+ Vm dp
Combining the above equations,
- RT ln xA =  pp+ Vm dp
For dilute solutions, ln xA may be replaced by ln (1-xB)  -xB
We may also assume that the pressure range in the integration
is so small that the molar volume of the solvent is a constant:
RT xB =  Vm
For dilute solutions, xB  nB / nA
nAVm = V
Thus, we have the van’t Hoff equation:
 V = nB RT
or,
 = [B] RT
 Activities

Real solvent A Real solute B

• The solvent activity

• The solute activity
Procedure:
1. Standard state and standard chemical potential (ideal-dilute)
2. Solvent or solute activity (real solution)
 The solvent activity

Chemical potential of an ideal solvent:

mA(l) = mA*(l) + RT ln ( pA / pA*) = mA*(l) + RT ln xA
Chemical potential of a real solvent:
mA(l) = mA*(l) + RT ln ( pA / pA*)
Activity: aA = pA / pA*
Activity coefficient: aA = gA xA
Standard chemical potential

mA(l) = mA*(l) + RT ln aA
= mA*(l) + RT ln xA + RT ln gA

Limit: aA  xA and gA  1 as xA  1
Standard state of the solvent: pure liquid solvent at 1 bar
 The solute activity

How to define the solute activity and standard state as

xB  0
Ideal-dilute solutions

Chemical potential of a solute that obeys Henry’s law:

mB(l) = mB*(l) + RT ln ( pB / pB*)
= mB*(l) + RT ln ( KB / pB*) + RT ln xB

standard chemical potential:

mB+(l) = mB*(l) + RT ln ( KB / pB*)

mB(l) = mB+(l) + RT ln xB

Standard state: a hypothetical state for xB  1

Standard chemical potential: mB(l) for xB  1
Real solutes

Chemical potential of a real solvent:

mB(l) = mB*(l) + RT ln ( pB / pB*)

Activity: aB = pB / KB

Activity coefficient: aB = gB xB

mB(l) = mB*(l) + RT ln (KB / pB*) + RT ln aB

= mB+(l) + RT ln aB
= mB+(l) + RT ln xB + RT ln gB

Limit: aB  xB and gB  1 as xB  0
Activities in terms of molalities
Dilute solution: xB =  mB / m0 ( m0 = 1 mol kg-1)

Chemical potential of a real solvent in a dilute solution:

mB(l) = mB+(l) + RT ln  + RT ln (mB / m0)
New standard chemical potential:
mB0(l) = mB+(l) + RT ln 
mB = mB0 + RT ln (mB / m0)
General real solution:

Activity: aB = gB mB / m0
Chemical potential: mB = mB0 + RT ln aB

Limit: gB  1 as mB  0
Table 7.3 Standard states (page 233)
---------------------------------------------------------------------------------
Component Basis Standard state Chemical potential Limits
--------------------------------------------------------------------------------------------------
Solvent Raoult Pure solvent m = m* + RT ln a g1 as x1
a= gx (pure solvent)

Solute Henry (1) Hypothetic m = m+ + RT ln a g1 as x0

state of pure a= gx
solute
(2) Hypothetic m = m0 + RT ln a g1 as m0
state of solute a = g m / m0
at molality m0

*Chemical Potential = Standard Chemical Potential

+ RT ln a
 Chemical Equilibrium

product
reactant
reactant

• Spontaneous chemical reactions

• The response of equilibria to the conditions
• Applications to selected systems
 Spontaneous Chemical Reactions

0 Extent of reaction 1

• The Gibbs energy minimum

• The composition of reactions at equilibrium
 The Gibbs energy minimum

Simplest Chemical equilibrium:

AB

Examples:
isomerization of pentane to 2-methylbutane
conversion of L-alanine to D-alanine
Extent of reaction  is a measure of the progress of the reaction.
We shall choose it so that ( for the reaction A  B ) pure A
corresponds to  = 0 and  = 1 signifies that 1 mol of A has been
converted to 1 mol of B. (page 273)
The extent of reaction
Suppose an infinitesimal amount d of A G
turns into B,
change in amount of A: dnA = - d
change in amount of B: dnB = + d
extent of reaction: 

At constant temperature & pressure, 0  / mol 1

dG = mA dnA + mB dnB
= - (mA - mB ) d

If at some stage mA > mB, then the reaction A  B is spontaneous;

If at some stage mA < mB, then the reaction A  B is spontaneous;
If at some stage mA = mB, then the reaction is at equilibrium and
neither A  B nor A  B is spontaneous.
The reaction Gibbs energy
Reaction Gibbs energy rG for A  B: G
the change in G when 1 mol A forms 1 mol
B at a fixed composition of the mixture

rG = ( G /  )p,T
= mB - mA 

*At equilibrium, rG = 0

Standard molar reaction Gibbs energy rG0 :
*rG0 = mA0 - mB0
i.e. the difference between the molar Gibbs energy of pure A
in its standard state and the molar Gibbs energy of pure B in
its standard state. rG0 is equal to the difference in the stan-
dard Gibbs energy of formation:
*rG0 = fG0(B) - fG0(A)
If A and B are gases, liquids or solids, their standard states
correspond to the pure substances at 1 bar.

If A and B are solutions, their standard states are those described

in “Activities • The properties of simple mixtures” (page 274)

The standard Gibbs energy of formation is the standard reaction

Gibbs energy for the formation of a compound from its elements
in their reference states. (page 154)
*The extent of reaction
If at some stage rG < 0, reaction A  B G
is spontaneous; rG<0
rG>0

If at some stage rG > 0, reaction A  B

is spontaneous;
rG = 0

If at some stage rG = 0, reaction A  B 

is in equilibrium;

Exergonic reaction (work-producing):  rG < 0

Endergonic reaction (work-consuming):  rG > 0
 The composition of reaction at equilibrium

Question:
what is the composition at equilibrium ?
Perfect gas equilibria AB
Assuming A and B are perfect gases, G

*rG = [mB0 + RT ln ( pB / pB0)]

- [mA0 + RT ln ( pA / pA0)]
= rG 0 + RT ln ( pB / pA)
= rG 0 + RT ln Q
Q = pB / pA 

At equilibrium, rG = 0
*RT ln K = - rG 0
K = (pB / pA )equilibrium (equilibrium constant)

For rG 0 > 0, K < 1 i.e. at equilibrium the partial pressure of A

exceeds that of B;
For rG 0 < 0, K > 1 i.e. at equilibrium the partial pressure of B
exceeds that of A.
Interpretation

Gibbs energy
rG0
Gibbs energy for no mixing:
nomixG = nAG0(A) + nBG0(B)
Gibbs energy of mixing:
mixG = nRT ( xA ln xA + xB ln xB ) 0
Extent of reaction
1

Change of chemical potentials for A  B:

mixG
rG = nomixG + mixG

The minimum in the Gibbs energy curve stems from the Gibbs
energy of mixing two gases
A special case of a reaction
Reaction: 2A + 3B  C + 2D
when reaction advances by d, the amount of reactants and
products change as:
dnA = -2 d dnB = -3 d dnC = + d dnD = + 2 d
The change of Gibbs energy:
dG = mA dnA + mB dnB + mC dnC + mD dnD
= (-2mA - 3mB + mC + 2mD) d
The reaction Gibbs energy:
rG = - 2mA - 3mB + mC + 2mD
= rG 0 + RT ln Q
The standard molar energy
*rG 0 = -2mA0 - 3mB0 + mC0 + 2mD0
Reaction quotient: Q = aC aD2 / aA2 aB3
Equilibrium constant: K = ( aC aD2 / aA2 aB3 )equilibrium
The general case of a reaction
General Reaction: 0 =  nJ J
when reaction advances by d, the amount of reactants and
products change as:
dnJ = nJ d
The change of Gibbs energy:
dG = (  nJ mJ ) d
The reaction Gibbs energy:
*rG =  nJ mJ
= rG 0 + RT ln Q
The standard molar energy
*rG 0 =  nJ mJ0
Reaction quotient
*Q =  aJnJ

Thermodynamic equilibrium constant:

*K = (  aJn )equilibrium
J
The relation between thermodynamic and practical
equilibrium constants
Answer: express the activity coefficients in terms of mole
fractions and molalities, i.e.
aJ = gJ xJ or aJ = gJ mJ / m0

A+BC+D
K = aC aD / aA aB = ( gC gD / gA gB ) ( mC mD / mA mB )
= Kg Km
 Km ( if Kg  1 )

*RT ln K = - rG 0
Origin of equilibrium constant
Equilibrium constant depends on
B temperature and overall energetics

Boltzmann Distribution

Boltzmann distribution does not

distinguish A and B

population
 The Response of Equilibria to the
Condition

• How equilibria respond to pressure

• The response of equilibria to temperature
 How equilibria respond to pressure
Equilibrium constant depends on rG 0 which is defined at a
single standard pressure and is thus a constant. Thus
( K / p )T = 0

Example, A  2B
K = pB2 / pA p0
pA increases much faster than pB

the extent of dissociation a of A into 2B

a = {1 / [ 1+ ( 4p / Kp0 ) ] }1/2

the amounts of A & B do depend on p

*Le Chatelier’s principle
A system at equilibrium, when subjected to a disturbance,
responds in a way that tends to minimize the effect of the
disturbance
 The response of equilibria to temperature
Le Chatelier’s principle predicts for an equilibrium system:
(1) when temperature is raised, it shifts in the endothermic
direction;
(2) when temperature is lowered, it shifts in the exothermic
direction.
Exothermic reactions:
increased temperature favours the reactants.

Endothermic reactions:
increased temperature favours the products.

Van’t Hoff equation

d ln K / dT = rH 0 / RT2
 The van’t Hoff Equation
Van’t Hoff equation
d ln K / dT = rH 0 / RT2
Increasing temperature,
(1) for exothermic reaction, dK / dT < 0
i.e. favours the reactants;

(2) for endothermic reaction, dK / dT > 0

i.e. favours the products.
Justification

ln K = - rG 0 / RT
Differentiation of ln K:
d ln K / dT = - ( 1 / R ) d (rG 0 / T) / dT
According to the Gibbs-Helmholtz equation:
[(G / T) / T]p = - H / T2
We have,
d (rG 0 / T) / dT = - rH0 / T2
Thus,
d ln K / dT = rH0 / RT2
Justification More reactant B

Higher temperature

population
 The value of K at different temperatures
Another form of van’t Hoff equation
d ln K / d(1/T) = - rH 0 / R
 d ln K = - (1 / R)  rH 0 d(1/T)
Assuming rH 0 varies slightly,
ln K2 - ln K1 = -(rH 0 / R) (1/T2 - 1/T1)
 Applications to Selected Systems

• The extraction of metals from their oxides

• Acids and bases
• Biological activity: thermodynamic of ATP
 The extraction of metals from their oxides
Metal reduction from its oxides:
(a) MO(s) + (1/2)C(s)  M(s) + (1/2)CO2(g)
(b) MO(s) + C(s)  M(s) + CO(g)
(c) MO(s) + CO(g)  M(s) + CO2(g)
Reference reactions:
(i) M(s) + (1/2)O2(g)  MO(s)
(ii) (1/2)C(s) + (1/2)O2(g)  (1/2)CO2(g)
(iii) C(s) + (1/2)O2(g)  CO(g)
(iv) CO(s) + (1/2)O2(g)  CO2(g)
Standard Gibbs energies of reduction:
(a) rG 0 = rG 0(ii) - rG 0(i)
(b) rG 0 = rG 0(iii) - rG 0(i)
(c) rG 0 = rG 0(iv) - rG 0(i)
Ellingham diagram (page 290)

-500
drG0 / dT = -rS0
Reaction (iii)
rG 0 / kJ mol-1

-300

Reaction (ii)

-100

Reaction (iv)
100
500 1500 2500

T / oC
 Acids and Bases

BrØnsted-Lowry Classification:

(1) an acid HA is a proton donor, HA  H+ + A-

(2) an base B is a proton acceptor, B + H+  BH+
Acid-base equilibria in water
Acid (HA) equilibrium in water
HA(aq) + H2O(l)  H3O+(aq) + A-(aq)
hydronium ion conjugated base
equilibrium constant:
K = a(H3O+) a(A-) / a(HA) a(H2O)

for dilute solution, a(H2O)  1, the acidity constant

Ka = a(H3O+) a(A-) / a(HA)

Base (B) equilibrium in water

B(aq) + H2O(l)  HB+(aq) + OH-(aq)
conjugated acid
Acid-base equilibria in water
BrØnsted equilibrium
Acid(aq) + H2O(l)  H3O+(aq) + Base(aq)
acidity constant
Ka = a(H3O+) a(Base) / a(Acid)

pKa value
pKa = - log Ka

Gibbs energy of proton transfer

rG 0 = - RT log Ka = 2.303 RT x pKa
Autoprotolysis and pH
Water is amphiprotic, which means that it can act as both
an acid and a base:
HF(aq) + H2O(l)  H3O+(aq) + F-(aq)
Acid Base
H2O(l) + NH3(aq)  NH4+(aq) + OH-(aq)
Acid Base
Autoprotolysis equilibrium
H2O(l) + H2O(aq)  H3O+(aq) + OH-(aq)
Acid Base
Autoprotolysis constant of water
Kw = a(H3O+) a(OH-) (=1.008 x 10-14 at 25oC)

pH scale: pH = - log a(H3O+)

pOH scale: pOH = - log a(OH-)
pKw value: pKw = - log Kw = pH + pOH
pH calculations
How to calculate the pH value of dilute aqueous solution ?

For very dilute aqueous solutions,

aJ  mJ / m0  [J] / (mol L-1)

where [J] is the molar concentration of J.

Equilibrium constant
Ka  [H3O+] [Base] / [Acid]

pH value may be determined using the above formula when

the value of Ka is given
Strong and Weak acids
Strong acid: a strong proton donor, virtually fully ionized
in solution, e.g.
HCl(aq) + H2O(l)  H3O+(aq) + Cl-(aq) virtually complete
Strong base: a strong proton acceptor, virtually fully ionized
in solution, e.g.
O-2(aq) + H2O(l)  2OH+(aq) virtually complete

Weak acid: a Bronsted acid, incompletely ionized in solution

with a positive pKa, e.g.
CH3COOH(aq) + H2O(l)  H3O+(aq) + CH3CO2-(aq)
Weak base: a Bronsted base, partially protonated, e.g.
NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq)
Strong acids and bases: the min. Gibbs energy of solution close
to the ionized products;
Weak acids and bases: the min. Gibbs energy of solution close
to the non-ionized reactants;
Acid-base titrations
Stoichiometric point (or equivalent point) at which a stoi-
chiometric amount of an acid has been added to a base.

In a titration of a strong acid with a strong base (or vice

versa) pH is barely affected.
pH = pOH = 7
In a titration of a weak acid with a strong base, pH changes:
the molar concentration H of hydronium ions is given by
VB / VA = [(Ka+H)(Kw-H2)+KwA0H] / [(Ka+H)(BH+H2-Kw)]

H: molar concentration of H3O+

VB, VA: volume of B and A, respectively, V = VB + VA
A0: intial molar concentration of A (before titration)
Ka : acidity constant, Kw: autoprotolysis constant
B: molar concentration of B
Justification
Strong base: MOH Weak Acid: HA
Charge neutral: [M+] + [H3O+] = [A-] + [OH-] (1)
total number of A groups (as HA and A- ) is constant: A0 VA
[HA] + [A-] = A = A0VA / (VA + VB)
The molar concentration of [M+] is BVB
[M+] = S = BVB / (VA + VB)
Ka = a(H3O+) a(A-) / a(HA)  [H3O+] [A-] / [HA]
Kw = a(H3O+) a(OH-)  [H3O+] [OH-]
[A-] = AKa / ( Ka + [H3O+] ) = AKa / ( Ka + H ) { [H3O+] = H }
Go back to (1):
H + BVB / (VA + VB) = A0VAKa / [(VA + VB)(Ka + H)] + Kw / H
The pH in the course of a weak acid-strong base titration
After the addition of some base (but before the stoichiometric
point is reached), the concentration of A- ions stems entirely
from the salt that is present, for the weak acid provides only
a few A- ions, [A-]  S = [M+]
Ka = a(H3O+) a(A-) / a(HA)  a(H3O+) S / ( A-S )
[HA] = A - S
pH = pKa - log ( A-S / S ) = pKa - log ([Acid] / [Base])
Henderson-Hasselbalch equation
When the molar concentrations of acid and salt are equal,
pH = pKa
When so much strong base has been added that the titration
has been carried well past the stoichiometric point, the pH is
controlled by the excess base
[H3O+]  Kw / [OH-] pH = pKa + log B’
where B’ is the molar concentration of excess base.
 *Summary of regions of pH curve of titration

pH = pKa + log B’
pH

pH = pKa - log (A’/ S) pH = 1/2pKa + 1/2pKw + 1/2 log S

pKa

Volume of titration
pH = 1/2pKa - 1/2log A0
Half-way to Stoichiometric
stoichiometric point
point
*Buffers and indicators

The slow variation of the pH in the vicinity of S=A’ (=A-S),

when the molar concentrations of the salt and acid are equal,
is the basis of buffer action, the ability of a solution to oppose
changes in pH when small amounts of strong acids and bases
are added to the solution.
Reason: (1) enough A- ions to remove the addition of H3O+
(2) enough HA molecules to react with extra base

The rapid change of pH near the stoichiometric point in a

titration is the basis of indicator detection.

An acid-base indicator is normally some large, water-soluble,

weakly acidic organic molecule which can exist as acid (HIn)
or conjugated base (In-) forms that differ in color.
 Biological activity: the thermodynamics of ATP

ATP (adenosine triphosphate) hydrolysis:

ATP(aq) + H2O(l)  ADP(aq) + Pi-(aq) + H3O+(aq)

rG = -30 kJ / mol

Proton transfer is involved in biological activities

Biological standard states
Conventional standard state of hydrogen ions (unit activity, pH=0)
is not appropriate to normal biological conditions.

Biological standard state: pH = 7, or neutral solution.

The relation between the thermodynamic & biological standard

Gibbs energies for a reaction of the form

A + nH+(aq)  P
is
rG = rG0 + 16.12 nRT
where, rG0 = m(P) - m(A) - n m(H+)
Note that there is no difference between the two standard values
if protons are not involve in the reaction (n=0)
Justification
The reaction Gibbs energy:
rG = m(P) - m(A) - nm(H+)
If all the species other than H+ are in their standard states:
rG = m(P) - m(A) - nm(H+)
Since
m(H+) = m(H+) + RT ln a(H+) = m(H+) - 2.303RT pH
Thus,
rG = m(P) - m(A) - n m(H+) + 2.33 nRT pH
= rG + 2.33 nRT pH
For biological standard state, pH = 7
rG = rG0 + 16.12 nRT
 Equilibrium electrochemistry

• Thermodynamic Properties of Ions in

Solution
• Electrochemical Cells
• Applications of Standard Potentials
 Thermodynamic Properties of Ions
in Solutions

cation

anion

• Thermodynamic functions of formation

• Ion activities
 Thermodynamic functions of formation

The standard enthalpy and Gibbs energy of a reaction

involving ions in solution are expressed in terms of standard
enthalpies and Gibbs energies of formation, which are used
exactly the same as those for neutral compounds.
Examples:
AgCl(s)  Ag+(aq) + Cl-(aq)
rG 0 = fG 0(Ag+,aq) + fG 0(Cl-,aq) - fG 0(AgCl,s)
Ag(s) + (1/2)Cl2(g)  Ag+(aq) + Cl-(aq)
rH 0 = fH 0(Ag+,aq) + fG 0(Cl-,aq)
The enthalpies of formation of ions

Ag(s) - e-  Ag+(aq) (1/2)Cl2(g) + e-  Cl-(aq)

Define that H+ has zero standard enthalpy of formation:

*fH 0(H+,aq) = 0 at all temperatures
This definition adjusts the actual values of the enthalpies of ions
all by a fixed amount. The adjusted enthalpies of ions may then
be determined from the standard enthalpies of reaction
Example
(1/2)H2(g) + (1/2)Cl2(g)  H+(aq) + Cl-(aq) rH 0 = - 167.16 kJ mol-1
fH 0(Cl-,aq) = rH 0 - fH 0(H+,aq) = - 167.16 kJ mol-1

Ag(s) + (1/2)Cl2(g)  Ag+(aq) + Cl-(aq) rH 0 = - 61.58 kJ mol-1

fH 0(Ag+,aq) = rH 0 - fH 0(Cl-,aq) = + 105.58 kJ mol-1
The Gibbs energies of formation of ions
The Gibbs energy of individual ion formation reactions, e.g.
Ag(s) - e-  Ag+(aq) (1/2)Cl2(g) + e-  Cl-(aq)

Define that H+ has zero standard Gibbs energy of formation:

*fG 0(H+,aq) = 0 at all temperatures
This definition adjusts the actual values of the Gibbs energies
of formation of ions all by a fixed amount. The adjusted Gibbs
energies of ions may then be determined from the standard
Gibbs energies of reactions
Example
(1/2)H2(g) + (1/2)Cl2(g)  H+(aq) + Cl-(aq) rG 0 = - 131.23 kJ mol-1
fG 0(Cl-,aq) = rG 0 - fG 0(H+,aq) = - 131.23 kJ mol-1

Ag(s) + (1/2)Cl2(g)  Ag+(aq) + Cl-(aq) rG0 = - 54.12 kJ mol-1

fG 0(Ag+,aq) = rG 0 - fG 0(Cl-,aq) = + 77.11 kJ mol-1
The entropies of ions in solution
Define that H+ has zero standard entropy:
*S 0(H+,aq) = 0 at all temperatures
This definition adjusts the actual values of the entropies of ions
all by a fixed amount. Thus, the entropies may be either positive
or negative.
Molar ion entropies vary as expected on the basis that they are
related by the degree to which the ions order water molecules
around them in the solution.

Small, highly charged ions induce local structure of water, and

disorder is decreased more than in the case of large, singly
charged ions.
 Ion activities

Dilute solutions of non-electrolytes:

solute activities can be replaced by molalities

Ionic solutions:
solute activities themselves must be used

Equilibrium constants K and Km (in terms of molalities)

K = Kg Km
The definition of activity
The chemical potential of a solute:
m = m0 + RT ln a

Activity and its coefficient: a = g m / mo

The activity coefficient g depends on the composition, molality,
and temperature of the solution. At low molalities, the activity
coefficient g tends towards 1

g  1 and a  m / mo as m  0

m = m0 + RT ln (m / mo ) + RT ln g
= mid + RT ln g
chemical potential of the ideal-dilute solution
Mean activity coefficients
A charge neutral solution contains univalent cations M+ (m+id )
and univalent anions X- (m-id).

For an ideal solution, the chemical potential :

Gid = m+id + m-id

For a real solution, the chemical potential :

G = m+ + m-
= m+id + m-id + RT ln g+ + RT ln g-
= Gid + RT ln g+g- Not separable experimentally
Define the mean activity coefficient: g = ( g+g-)1/2
m+ = m+id + RT ln g
m- = m-id + RT ln g
Mean activity coefficients
Compound MpXq dissolves to form a solution of p cations and
q anions. The total Gibbs energy of ions:
G = pm+ + qm-
= Gid + pRT ln g+ + qRT ln g-
Define the mean activity coefficient:
g = ( gp+ gq-)1/s s=p+q
*m+ = m+id + RT ln g
*m- = m-id + RT ln g
The Debye-Hückel limiting law
Ionic atmosphere Lower energy

cation

anion

Debye-Hückel limiting Law:

log g = - |z+ z-| A (I / m0)1/2
where A = 0.509 for an aqueous solution at 25oC(it depends on
permittivity and temperature), and I is the ionic strength
I = (1/2) i zi2 mi
For solutions consisting of two types of ions
*I = (1/2) ( m+ z+2 + m- z-2 )
Limiting: applicable in the limit of arbitrarily low molalities
The Extended Debye-Hückel law

When the ionic strength of the solution is too high for the
limiting law to be valid, it is found that the activity coefficient
may be estimated from

Extended Debye-Hückel Law:

log g = - ( |z+ z-| A (I / m0)1/2 ) / ( 1 + B (I / m0)1/2 )
where B is another dimensionless constant, is regarded as an
adjustable empirical parameter.
 Electrochemical Cells
Electrodes

Electrochemical cell
Electrode
compartment
Electrolyte

Two types of electrochemical cell

Galvanic cell: produces electricity as a result of spontaneous
reactions occurring inside it
Electrolytic cell: where a non-spontaneous reaction is driven
by an external source of current
 Half-reactions and electrodes
Half-reactions
Any redox reaction may be expressed in terms of two half-
reactions, which are conceptual reactions showing the loss
and gain of electrons. Reductant
Oxidant Cu2+(aq) + Zn(s)  Cu(s) + Zn2+(aq)
can be expressed as sum of the following two half-reactions:
(1) Reduction of Cu2+: Cu2+(aq) + 2e-  Cu(s)
Redox
(2) Oxidation of Zn: Zn(s)  Zn (aq) + 2e
2+ -
couple
or in common practice, may be expresses as the difference
of the two half-reductions: [Ox/Red]
(3) Reduction of Cu2+: Cu2+(aq) + 2e-  Cu(s) [Cu2+/Cu]
(4) Reduction of Zn2+: Zn2+(aq) + 2e-  Zn(s) [Zn2+/Zn]
the reaction quotient Q for (3) and (4):
(3) Q = 1 / a(Cu2+)
(4) Q = 1 / a(Zn2+)
Reactions at electrodes
General reduction half-reaction:
Ox + ne-  Red
General oxidation half-reaction:
Red  Ox + ne-
Anode reaction (oxidation): Red1  Ox1 + ne-
Cathode reaction (reduction): Ox2 + ne-  Red2

Anode e- Cathode
Red1  Ox1 + ne-

Ox2 + ne-  Red2

Varieties of electrodes
Metal / metal-ion electrode: consists of a metal in contact with
a solution of one of its salts (e.g. copper in contact w/ aqueous
solution of Cu2+), denoted as M | Mn+(aq) (M is metal, | is the
interface between two phases)
Gas electrode: in which a gas is in equilibrium with a solution
of its ions in the presence of inert metal. The inert metal (which
is often platinum) acts as a source or sink of electrons. (e.g.
Hydrogen electrode, in which hydrogen is bubbled through a
solution of H+ and redox couple is H+ / H2; The electrode is
denoted as Pt | H2(g) | H+(aq)

Metal / insoluble-salt electrode: consists of a metal M covered

by a porous layer of insoluble salt MX with the immersed in a
solution containing X- ions, denoted as M | MX | X- (e.g. silver
| silver chloride electrode)
 Varieties of cells

Ag/AgCl
Hydrogen Electrodes
electrode
electrode

HCl

Electrolyte

Simplest type of cell: single electrolyte

Pt | H2(g) | HCl(aq) | AgCl(s) | Ag
 Zn Electrodes Cu

Electrolyte B
ZnSO4
Electrolyte A
CuSO4

Daniell cell: different electrolytes

Zn(s) | ZnSO4(aq) CuSO4(aq) | Cu(s)

denotes the liquid junction between two electrolytes

 Salt bridge
Pt
Pt

HCl HCl

Same Type of Electrolyte

Electrolyte concentration cell:

same type of electrolytes but different concentrations
Pt | H2(g) | HCl(aq,m1) || HCl(aq,m2) | H2(g) | Pt
denotes a liquid junction where the junction potential has been eliminated
 Same Type of Electrode

Electrolyte

Electrode concentration cell:

same type of electrode but different concentration
 Salt bridge
Cu
Zn

ZnSO4 CuSO4

Zn(s) | ZnSO4(aq) || CuSO4(aq) | Cu(s)

The cell potential
Cell potential (V) : the potential difference between the two
electrodes
when the cell potential is large, a given number of electrons
travelling between the electrodes can do a large amount of
work;
when the cell potential is small, the same number of electrons
can only do a small amount of work.
The maximum amount work:
we,max = G at constant T and P
The cell operated reversibly at a constant composition when it
is balanced by an exactly opposing source of potential. The
resulting potential difference is called the zero-current cell
potential E (electromotive force or emf of the cell)
*Relation between E and rG : - n F E = rG
Faraday’s constant F = 96.485 kC mol-1
Justification
At constant temperature and pressure, the change in G is,
dG = J mJ dnJ = J nJ mJ d
The reaction Gibbs energy rG at the specified composition:
rG = ( G /   )p,T = J nJ mJ
dG = rG x d
The maximum work that the reaction can do is therefore,
dwe = rG x d
The total charge transported between the electrodes is
-n eNA d = -n F d
Therefore,
dwe = rG x d = -n F E x d
rG = -n F E
The Nernst equation

we relate the zero-current cell potential to the activities of the participants

The reaction Gibbs energy:

rG = rG 0 + RT ln Q
with the reaction quotient Q =  aJn J

E = - ( rG 0 / n F ) - ( RT ln Q / n F )
*Defining the standard cell potential E0
*- n F E0 = rG0
E = E0 - ( RT / n F ) ln Q

At 25oC, RT/F = 25.7 mV, thus

E = E0 - (25.7 mV / n ) ln Q
*Concentration cells
Nernst equation can be used to evaluate the potential of an
electrolyte concentration cell

Consider the cell

M | M+(aq,L) || M+(aq,R) | M
where the solutions L and R have different molalities. Reaction
M+(aq,L)  M+(aq,R) Q = aL / aR n = 1

The standard cell potential is zero, because a cell cannot drive a

current through a circuit when the two electrode compartments
are identical, i.e. rG0 = 0
E = - ( RT / F ) ln (aL / aR)
 - ( RT / F ) ln (mL / mR)
 Standard potentials
It is not possible to measure the contribution of a single
electrode, we may define the potential of one of the electrodes
as having a zero potential and then assign values of others
*Standard hydrogen electrode (SHE):
Pt | H2(g) | H+(aq) at all temperatures

*Standard potential E0 of another couple may be assigned

by constructing a cell in which it is the right-hand electrode
and the standard hydrogen electrode is left-hand electrode
e.g. Pt | H2(g) | H+(aq)||Ag+(aq) | Ag(s)

E0(Ag+ / Ag) = E0 = 0.80 V at 25oC

Similarily, E0(AgCl / Ag, Cl-) = 0.22 V

 The standard potential of a cell in terms of
reduction potentials

*Standard potential of a cell formed from any two electrodes

can be calculated by taking the difference of their standard
potentials. e.g.
Ag(s) | Ag+(aq) || Cl-(aq) | AgCl(s) | Ag(s)
is equivalent to two cells joined back-to-back:
Ag(s) | Ag+(aq) || Cl-(aq) || H+(aq)| H2(g) | Pt
Pt | H2(g) | H+(aq)|| Cl-(aq) | AgCl(s) | Ag(s)
The overall potential of the composite cell:
E0= E0(AgCl/Ag, Cl-) - E0(Ag+ / Ag) = - 0.58 V
The composition dependence of individual potentials
Overall cell potential dependence on composition may be described
by the Nernst equation. Similar equations may be for individual
reduction potentials. e.g. the potential of Ag+ / Ag electrode at an
arbitrary Ag+ ion activity is given by the expression
E(Ag+/Ag) = E0(Ag+/Ag) - (RT /F) ln Q
where Q is the reaction quotient for the half-reaction
Ag+(aq) + e-  Ag(s) Q = 1 / a(Ag+)

Can we measure the standard potential E0 ?

Justification
Consider a cell in which the left-hand electrode is a standard
hydrogen electrode: Pt | H2(g) | H+(aq) || Ag+(aq) | Ag(s)
The reaction: H2(g) + 2 Ag+(aq)  2 H+(aq) + Ag(s)
Q = a(H+)2 / [ (fH2 / p 0) a(Ag+)2] n = 2
The Nernst equation:
E = E0 - ( RT / 2 F ) ln Q = E0 (Ag+/Ag)- ( RT / 2 F ) ln Q
When the hydrogen electrode has its standard composition,
a(H+) = 1, and fH2 = p 0 ; Q = 1 / a(Ag+)2
Cell potential can be regarded as arising solely from electrode Ag+/Ag
E(Ag+/Ag) = E0 (Ag+/Ag)- ( RT / 2 F ) ln (1 / a(Ag+)2)
= E0 (Ag+/Ag)- ( RT / F ) ln (1 / a(Ag+))
The measurement of standard reduction potentials
Measurement is made on the Harned cell:
Pt | H2(g) | HCl(aq) | AgCl(s) | Ag(s)
1/2 H2(g) + AgCl(s)  HCl + Ag(s)
E = E0(AgCl/Ag, Cl-) - (RT / F) ln [a(H+)2a(Cl-) / (fH2 / p0)1/2]
Set fH2 = p0 and expressing a in terms of g
E = E0 (AgCl/Ag, Cl-)- (RT / F) ln (m/m0)2 - (2RT / F) ln g
From the Debye-Huckel limiting law,
E + (2RT/F) ln(m/m0) = E0(AgCl/Ag, Cl-) + (2A’RT / F) (m/m0)1/2

Plotting the left hand side against m1/2 & extrapolated to m = 0,

we may obtain the value of E0(AgCl/Ag, Cl-)
The measurement of activity coefficients
Once the standard potential of an electrode in a cell is known,
the activities of the ions with respect to which it is reversible can
be determined by measuring the cell potential with the ions at
the concentration of interest, e.g. the mean activity coefficient of
the ions in hydrochloric acid of molality m is obtained as follows,

ln g = [ E0 (AgCl/Ag, Cl-) - E ] / (2RT / F) - ln (m/m0)

Once E has been measured.

One Summer Research Student:

Requirement: word processing including MS Power Point;

knowledge of Web including Java is preferred.
Duration: two months
Salary: HK$ 7,000 - 8,000 per month
 Applications of standard potentials

• The electrochemical series

• Solubility constant
• The measurement of pH and pK
• Potentiometric titrations
• Thermodynamic functions from cell
potential measurements