THERMODYNAMICS.

Elements of Physical Chemistry. By P. Atkins

Dr. H.A. Ellis
18/1/05

Concerned with the study of
transformation of energy:
Heat work
CONSERVATION OF ENERGY states that:
Energy can neither be created nor destroyed in chemical
reactions. It can only be converted from one form to the other.

UNIVERSE
System part of world have special interest in
Surroundings where we make our observations

Open system Closed system Isolated system
Example:

matter
energy energy not matter matter
Energy
If system is themally isolated called Adiabatic system eg: water
in vacuum flask.
WORK and HEAT
Work transfer of energy to change height of the weight in
surrounding eg: work to run a piston by a gas.

Heat transfer of energy is a result of temperature difference
between system and surrounding eg:

HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H
2
O
(l)
- heat given off.


If heat released to surroundings exothermic.
If heat absorbed by surroundings endothermic.
Example: Gasoline, 2, 2, 4 trimethylpentane
CH
3
C(CH
3
)
2
CH
2
CH(CH
3
)CH
3
+ 25/2 O
2
8CO
2(g)
+H
2
O
(l)

5401 kJ of heat is released (exothermic)


Where does heat come from?
From internal energy, U of gasoline. Can represent chemical reaction:

U
initial
= U
final
+ energy that leaves system (exothermic)
Or
U
i
= U
f
energy that enters system (endothermic)

Hence, FIRST LAW of THERMODYNAMICS (applied to a closed
system)
The change in internal energy of a closed system is the energy
that enters or leaves the system through boundaries as heat or
work. i.e.
U = q +w
U = U
f
U
i
q heat applied to system
W work done on system
When energy leaves the system, U = -ve i.e. decrease internal
energy
When energy enter the system, U = +ve i.e. added to internal
energy


Different types of energies:
1. Kinetic energy = mv
2
(chemical reaction) kinetic energy

(KE) k T (thermal energy) where k = Boltzmann constant


2. Potential energy (PE) = mgh energy stored in bonds


Now, U = KE + PE
3. Work (W)
w = force distance moved in direction of force
i.e. w = mg h = kg m s
-2
m = kg m
2
s
-2
(m) (g) (h)

1 kg m
2
s
-2
= 1 Joule


- Consider work work against an opposing force, eg: external
pressure, p
ex
. Consider a piston
Piston

Pex
pressure (P)
pex
A = area of piston
P
h
h is distance moved
w = distance opposing force
w = h (p
ex
A) = p
ex
hA

Work done on system = p
ex
V
V change in volume (V
f
V
i
)

Work done by system = -p
ex
V
Since U is decreased

Example:
C
3
H
8(g)
+ 5 O
2(g)
3CO
2(g)
+ 4H
2
O
(l)
at 298 K 1 atm

(1 atm = 101325 Pa), -2220 kJ = q


What is the work done by the system?
For an ideal gas;
pV = nRT (p = p
ex
)
n no. of moles
R gas constant
T = temperature
V volume
p = pressure
V= nRT/p or V
i
= n
i
RT/p
ex

6 moles of gas:
V
i
= (6 8.314 298)/ 101325 = 0.1467 m
3

3 moles of gas:
V
f
= (3 8.314 298)/ 101325 = 0.0734 m
3

work done = -p
ex
(V
f
V
i
)
= -101325 (0.0734 0.1467) = +7432 J



NB: work done = - p
ex
(n
f
RT/p
ex
n
i
RT/p
ex
)

= (n
f
n
i
) RT

Work done = -n
gas
RT

i.e. work done = - (3 6) 8.314 298 = + 7432.7 J

Can also calculate U
U = q +w q = - 2220 kJ
w = 7432.7 J = 7.43 kJ

U = - 2220 + 7.43 = - 2212.6 kJ
NB:
q
p
= U why?

Only equal if no work is done i.e. V = 0

i.e. q
v
= U

Example: energy diagram
C
3
H
8
+ 5 O
2
(U
i
)
3CO
2
+ 4H
2
O
(l)
(U
f
)
U
U
progress of reaction
reaction path
Since work done by system = p
ex
V

System at equilibrium when p
ex
= p
int
(mechanical equilibrium)

Change either pressure to get reversible work i.e.

p
ex
> p
int
or p
int
> p
ex
at constant temperature by an infinitesimal
change in either parameter
For an infinitesimal change in volume, dV
Work done on system = pdV

For ideal gas, pV = nRT

p = nRT/ V
work = p dV = nRT dV/ V

= nRT ln (V
f
/V
i
) because }dx/x = ln x
Work done by system= -nRT ln(V
f
/V
i
)


}
Vf
Vi
}
Vf
Vi
Enthalpy, H


Most reactions take place in an open vessel at constant
pressure, p
ex
. Volume can change during the reaction
i.e. AV = 0 (expansion work).

Definition: H = q
p
i.e. heat supplied to the system at
constant pressure.



Properties of enthalpy


Enthalpy is the sum of internal energy and the product of pV of
that substance.

i.e H = U + pV (p = p
ex
)

Some properties of H

H
i
= U
i
+ pV
i
H
f
= U
f
+ pV
f

H
f
H
i
= U
f
U
i
+p(V
f
V
i
)
or
AH = AU + p AV
Since work done = - p
ex
AV



AH = (- p
ex
AV + q) +p

AV
(p
ex
= p)


AH = ( -p AV + q) + p AV = q

AH = q
p

suppose p and V are not constant?
AH = AU + A( pV) expands to:

AH = AU + p
i
AV + V
i
AP + (AP) (AV)

i.e. AH under all conditions.

When Ap = 0 get back

AH = AU + p
i
AV AU + p AV
When AV = 0:
AH = AU + V
i
Ap

Enthalpy is a state function.
lattitude
l
o
n
g
i
t
u
d
e
A
B
path 1
path 2
- does not depend on the path taken
NB: work and heat depend on the path taken and are written as
lower case w and q. Hence, w and q are path functions. The
state functions are written with upper case.


eg: U, H, T and p (IUPAC convention).
Standard States
By IUPAC conventions as the pure form of the substance at 1 bar
pressure (1 bar = 100,000 Pa).


What about temperature?
By convention define temperature as 298 K but could be at any
temperature.
Example:
C
3
H
8(g)
+ 5 O
2(g)
3CO
2(g)
+ 4H
2
O
(l)


at 1 bar pressure, q
p
= - 2220 kJmol
-1
.

Since substances are in the pure form then can write

AH
u
= - 2220 kJ mol
-1
at 298 K

u represents the standard state.
H
2(g)
H
(g)
+ H
(g)
, AH
u
diss
= +436kJmol
-1

H
2
O
(l)
H
2
O
(g)
, AH
u

vap
= +44.0 kJmol
-1



Calculate AU
u
for the following reaction:

CH
4(l)
+ 2 O
2(g)
CO
2(g)
+ 2H
2
O
(l)
, AH
u
= - 881.1kJmol
-1
AH = AU

+ A(pV)
= AU + p
i
AV + V
i
Ap + Ap AV

NB: p = 1 bar, i.e. Ap = 0
AH
u
=

AU
u
+ p
i
AV


Since -p
i
AV = - AnRT,


AU
u
= AH
u
- AnRT
calculation


AU
u
= - 881.1 ((1 2)(8.314) 298)/ 1000
= - 881.1 (-1)(8.314)(0.298) = - 2182.99 kJ mol
-1
STANDARD ENTHALPY OF FORMATION, AH
f
u
Defined as standard enthalpy of reaction when substance is formed
from its elements in their reference state.

Reference state is the most stable form of element at 1 bar
atmosphere at a given temperature eg.
At 298 K Carbon = C
graphite
Hydrogen = H
2(g)
Mercury = Hg
(l)
Oxygen = O
2(g)
Nitrogen = N
2(g)
NB: AH
f
u
of element = 0 in reference state

Can apply these to thermochemical calculations
eg. Can compare thermodynamic stability of substances in
their standard state.

From tables of AH
f
u
can calculate AH
u
f rxn
for any reaction.


Eg. C
3
H
8 (g)
+ 5O
2(g)
3CO
2(g)
+ 4H
2
O
(l)
Calculate AH
u
rxn
given that:
AH
u
f
of C
3
H
8(g)
= - 103.9 kJ mol
-1
AH
u
f
of O
2(g)
= 0 (reference state)
AH
u
f
of CO
2(g)
= - 393.5 kJ mol
-1
AH
u
f
of H
2
O
(l)
= - 285.8 kJ mol
-1

AH
rxn
= En AH
u
(products)- En AH
u
(reactants)
AH
u
f
(products) = 3 (- 393.5) + 4 (- 285.8)
= - 1180.5 -1143.2 = - 2323.7 kJ mol
-1

AH
u
f
(reactants) = - 103.9 + 5 0 = - 103.9 kJ mol
-1

AH
u
rxn
= - 2323.7 (- 103.9) = - 2219.8 kJ mol
-1

= - 2220 kJ mol
-1




Answer same as before. Eq. is valid.
Suppose: solid gas (sublimation)
Process is: solid liquid gas
AH
sub
= AH
melt
+ AH
vap

Ie. AH ( indirect route) =
.
AH ( direct route)

Hess Law
- the standard enthalpy of a reaction is the sum of the standard
enthalpies of the reaction into which the overall reaction may be
divided. Eg.
C
(g)
+ O
2(g)
CO
(g)
, AH
u
comb
=? at 298K

From thermochemical data:
C
(g)
+O
2

(g)
CO
2(g)
AH
u
comb
=-393.5 kJmol
-
1
.(1)
CO
(g)
+1/2 O
2 (g)
CO
2(g),
AH
u
comb
= -283.0 kJ mol
-
1
. (2)
Subtract 2 from 1 to give:
C
(g)
+ O
2 (g)
CO
(g)
1/2 O
2

(g)
CO
2

(g)
CO
2

(g)
C
(g)
+ O
2

(g)
CO
(g)
, AH
u
comb
= -393.5
(-283.0) = - 110.5 kJ mol
-1


Bond Energies
eg. C-H bond enthalpy in CH
4

CH
4

(g)
C
(g)
+ 4 H
(g)
, at 298K.
Need: AH
f
u
of CH
4 (g)
=- 75 kJ mol
-1
AH
f
u
of H
(g)
= 218 kJ mol
-1
AH
f
u
of C
(g)
= 713 kJ mol
-1
AH
u
diss
= E nAH
f

u
(products)

- E nAH
f
u
( reactants)

= 713 + ( 4x 218) (- 75) = 1660 kJ
mol
-1

Since have 4 bonds : C-H = 1660/4 = 415
kJ mol
-1

Variation of AH
u
with temperature
Suppose do reaction at 400 K, need to know
AH
u
f
at 298 K for comparison with literature value. How?

As temp. AH
u
m
ie. AH
u
m
o T

AH
u
m
= C
p
,
m
A T where C
p
,
m
is the molar

heat capacity at constant pressure.

C
p
,
m
= AH
u
m
/ AT = J mol
-1
/ K
= J K
-1
mol
-1
A H
T2
= A H
T1
+ A C
p
( T
2
- T
1
)
Kirchoffs equation.
and
A C
p
= En C
p
(products)- EnC
p
(reactants)


For a wide temperature range: AC
p
dT between T
1
and T
2
.
Hence : q
p
= C
p
( T
2
- T
1
) or AH = C
p
AT and.

qv = C
v
( T
2
T
1
) or C
v
AT = AU
ie. C
p
= AH / AT ; C
v
=AU /AT
For small changes:

C
p
= dH / dT ; C
v
= du / dT

For an ideal gas: H = U + p V
For I mol: dH/dT = dU/dT + R
C
p
= C
v
+ R
C
p
/ C
v
= ( Greek gamma)
Work done along isothermal paths
Reversible and Irreversible paths
ie AT =0 ( isothermal)

pV = nRT= constant

Boyles Law : p
i
V
i
=p
f
V
f

Can be shown on plot:
pV diagram
P
V
P
i
v
i
P
f
v
f
pV
= nRT = constant
Work done = -( nRT) dV/V

= - nRT ln (V
f
/V
i
)

Equation is valid only if : p
i
V
i
=p
f
V
f
and therefore: V
f
/V
i
= p
i
/p
f
and

Work done = -( nRT) ln (p
i
/p
f
) and follows the path shown.


pV diagram


An irreversible path can be
followed: Look at pV
diagram again.

V
P
Isothermal reversible process
(ie. at equlb. at every stage
of the process)
Irreversible reaction
P
i
V
i
P
f
V
f
An Ideal or Perfect Gas
NB
For an ideal gas, Au = 0

Because: AU o KE + PE
o k T + PE (stored in bonds)

Ideal gas has no interaction between molecules (no bonds broken
or formed)

Therefore Au = 0 at AT = 0

Also AH = 0 since A(pV) = 0 ie no work done

This applies only for an ideal gas and NOT a chemical reaction.
Calculation
eg. A system consisting of 1mole of perfect gas at 2 atm and
298 K is made to expand isothermally by suddenly reducing the
pressure to 1 atm. Calculate the work done and the heat that
flows in or out of the system.
w = -p
ex
AV = p
ex
(V
f
-V
i
)
V
i
= nRT/p
i
= 1 x 8.314 x (298)/202650
= 1.223 x 10
-2
m
3

V
f
= 1 x 8.314 x 298/101325 = 2.445 x 10
-2
m
3

therefore, w = -p
ex
(V
f
- V
i
)
= -101325(2.445-1.223) x 10
-2
= -1239 J


AU = q + w; for a perfect gas AU = 0
therefore q = -w and
q = -(-1239) = +1239 J



Work done along adiabatic path
ie q = 0 , no heat enters or leaves the system.
Since AU = q + w and q =0
AU = w
When a gas expands adiabatically, it cools.
Can show that: pV

= constant, where ( C
p
/C
v
= )
and: p
i
V
i

= p
f
V
f

and since:
-p dV = C
v
dT

Work done for adiabatic path = C
v
(T
f
- T
i
)
For n mol of gas: w = n C
v
(T
f
T
i
)
Since p
i
V
i

= p
f
V
f



p
i
V
i

/T
i

= p
f
V
f

/ T
f

T
f
= T
i
(V
i
/V
f
)
-1
w =n C
v
{ ( T
i
( V
i
/ V
f
)
-1
T
i
}

An adiabatic pathway is much steeper than pV = constant
pathway.


Summary
p
i
V
i
= p
f
V
f
for both reversible and irreversible
Isothermal processes.
For ideal gas: For AT =0, AU = 0, and AH=0
For reversible adiabatic ideal gas processes:
q=0 , pV

= constant and
Work done = n C
v
{ ( T
i
( V
i
/ V
f
)
-1
T
i
}


p
i
V
i

= p
f
V
f

for both reversible and irreversible adiabatic ideal

gas.
2
nd
Law of Thermodynamics
Introduce entropy, S (state function) to explain spontaneous

change ie have a natural tendency to occur- the apparent
driving force of spontaneous change is the tendency of energy
and matter to become disordered. That is, S increases on
disordering.


2
nd
law the entropy of the universe tends to increase.
Entropy

AS = q
rev
/T ( J K
-1
) at equilibrium

AS
isolated system
> 0 spontaneous change

AS
isolated system
< 0 non-spontaneous change

AS
isolated system
= 0 equilibrium



Properties of S
If a perfect gas expands isothermally from
V
i
to V
f
then since AU = q + w = 0
q = -w ie
q
rev
= -w
rev
and
w
rev
= - nRT ln ( V
f
/V
i
)
At eqlb., AS =q
rev
/T = - q
rev
/T = nRln (V
f
/V
i
)
ie AS = n R ln (V
f
/V
i
)

Implies that AS 0 ( strange!)
Must consider the surroundings.

Surroundings

AS
total
= AS
system
+ AS
surroundings

At constant temperature surroundings give heat to the system
to maintain temperature.
surroundings is equal in magnitude to heat gained or loss but
of opposite sign to make

AS = 0 as required at eqlb.

Rem: dq = C
v
dT and
dS = dq
rev
/ T
dS = C
v
dT/ T and
AS = C
v
dT /T between T
i
and T
f
AS = C
v
ln ( T
f
/ T
i
)
When T
f
/ T
i
> 1 , AS is +ve
eg. L G , AS is +ve
S L , AS is +ve and since q
p
= AH
AS
melt
= AH
melt
/ T
melt
and
AS
vap
= AH
vap
/ T
vap


Third Law of Thermodynamics
eg. Standard molar entropy, AS
u
m
The entropy of a perfectly
crystalline substance is zero at T = 0

AS
u
m
/ J K
-1
at 298 K

ice 45
water 70 NB. Increasing disorder
water vapour 189
For Chemical Reactions:
AS
u
rxn =
E n AS
u

(products) - E n AS
u

( reactants)

eg. 2H
2 (g)
+ O
2( g)
2H
2
O
( l )
, AH
u
= - 572 kJ mol
-1

Calculation
Ie surroundings take up + 572kJ mol
-1
of heat



AS
u
rxn
= 2AS
u
(H
2
O
l
)

- (2 AS
u

(H
2g
) + AS
u

(O
2g
) )
= - 327 JK
-1
mol
-1
( strange!! for a spontaneous
reaction; for this AS
u
is + ve. ).
Why? Must consider S of the surroundings also.
AS
total
= AS
system
+ AS
surroundings
AS
surroundings
= + 572kJ mol
-1
/ 298K = + 1.92 x 10
3
JK
-1
mol
-1

AS
total
=( - 327 JK
-1
mol
-1
) + 1.92 x 10
3
= 1.59 x 10
3
JK
-1
mol
-1
Hence for a spontaneous change, AS > 0



Free Energy, G
Is a state function. Energy to do useful work.
Properties
Since AS
total
= AS
system
+ AS
surroundings
AS
total
=

AS - AH/T at const. T&p
Multiply by -T and rearrange to give:
-TAS
total
= - T AS + AH and since AG = - T AS
total

ie. AG = AH - T AS

Hence for a spontaneous change: since AS is + ve, AG = -ve.


Free energy



ie. AS > 0, AG < 0 for spontaneous change ;
at equilibrium, AG = 0.

Can show that : (dG)
T,p
= dw
rev
( maximum work)

AG = w (maximum)
Properties of G
G = H - T S
dG = dH TdS SdT
H = U + pV
dH = dU + pdV + Vdp
Hence: dG = dU + pdV + Vdp TdS SdT
dG = - dw + dq + pdV + Vdp TdS SdT

dG = Vdp - SdT
For chemical Reactions:
For chemical reactions

AG
u
=E n G
u
(products) - E n G
u
(reactants)

and


AG
u
rxn
= AH
u
rxn
- T AS
u
rxn
Relation between AG
u
rxn
and position of
equilibrium
Consider the reaction: A = B

AG
u
rxn
= G
u
B
- G
u
A

If G
u
A
> G
u
B
, AG
u
rxn
is ve ( spontaneous rxn)

At equilibrium, AG
u
rxn
= 0.

ie. Not all A is converted into B; stops at equilibrium point.
Equilibrium diagram
For non-spontaneous rxn. GB > GA,
AG is + ve
Gas phase reactions
Consider the reaction in the gas phase:
N
2(g)
+ 3H
2(g)
2NH
3(g)

Q =( pNH
3
/ p
u
)
2
/( ( pN
2
/ p
u
) (pH
2
/ p
u
)
3 )
where :

Q = rxn quotient ; p = partial pressure and p
u
= standard
pressure = 1 bar
Q is dimensionless because units of partial pressure cancelled
by p
u
.
At equilibrium:
Q
eqlb
= K = (( pNH
3
/ p
u
)
2
/ ( pN
2
/ p
u
) (pH
2
/ p
u
)
3
)eqlb
Activity ( effective concentration)


Define: a
J
= p
J
/ p
u
where a = activity or effective
concentration.
For a perfect gas: a
J
= p
J
/ p
u

For pure liquids and solids , a
J
= 1
For solutions at low concentration: a
J
= J mol dm
-3
K = a
2
NH3
/ a
N2
a
3
H2
Generally for a reaction:
aA + bB cC + dD

K = Q
eqlb
= ( a
c
C
a
d
D
/ a
a
A
a
b
B
)
eqlb
= Equilibrium constant


Relation of AG with K
Can show that:

AG
rxn
= AG
u
rxn
+ RT ln K

At eqlb., AG
rxn
= 0

AG
u
rxn
= - RT ln K

Hence can find K for any reaction from thermodynamic data.
Can also show that:

ln K = - AG
u
/ RT

K = e
- AGu / RT


eg
H
2 (g)
+ I
2 (s)
= 2HI
(g)
, AH
u
f HI
= + 1.7 kJ mol
-1
at 298K;
AH
u
f

H2
=0 ; AH
u
f

I 29(s)
= 0
calculation

AG
u
rxn
= 2 x 1.7 = + 3.40 kJ mol
-1

ln K = - 3.4 x 10
3
J mol
-1
/ 8.314J K
-1
mol
-1
x 298K
= - 1.37
ie. K = e
1.37
= 0.25

ie. p
2

HI
/ p
H2
p
u
=0.25 ( rem. p
u
= 1 bar; p
u 2
/ p
u
= p
u
)

p
2

HI
= p
H2
x 0.25 bar

Example: relation between K
p
and K
Consider the reaction:
N
2

(g)
+ 3H
2

(g)
= 2NH
3 (g)

K
p
=( p
NH3
/ p
u
)
2
/ ( p
N2
/ p
u
)( p
H2
/ p
u
)
3
and

K = [( p
NH3
/ p
u
)
2
/ ( p
N2
/ p
u
)( p
H2
/ p
u
)
3
]
eqlb

K
p
= K (p
u
)
2
in this case. ( Rem: (p
u
)
2
/ (p
u
)
4
= p
u -2
For K >> 1 ie products predominate at eqlb. ~ 10
3

K<< 1 ie reactants predominate at eqlb. ~ 10
-3

K ~ 1 ie products and reactants in similar amounts.

Effect of temperature on K
Since AG
u
rxn
= - RT ln K = AH
u
rxn
- TAS
rxn
ln K = - AG
u
rxn
/ RT = - AH
u
rxn
/RT + AS
rxn
u
/R

ln K
1
= - AG
u
rxn
/ RT
1
= - AH
u
rxn
/RT
1
+ AS
rxn
u
/R

ln K
2
= - AG
u
rxn
/ RT
2
= - AH
u
rxn
/ RT
2
+ AS
rxn
u
/ R

ln K
1
ln K
2
= - AH
u
rxn
/ R ( 1/ T
1
- 1/ T
2
) 0r

ln ( K
1
/ K
2
) = - AH
u
rxn
/ R ( 1/ T
1
- 1/ T
2
) vant Hoff equation