THERMODYNAMICS II

Chemical Reaction
Equilibria
1
Recap - Lewis Rule

fˆi v  y iˆ i P

ˆ iv   iv

fˆi v  y l  iv P or fˆi v  y i f i

2
 Recap - Lewis Rule
 For a binary mixture of species a & b from the van der
Waals EOS

ˆf v  y f v exp a 
 a  a 2 y2P 
b b

a a a
  RT  2

[130]

 1. Low pressure or high temperature

 2. There is large excess of component a (yb is small)
 3. The chemical nature of a is similar to b (aa≈ab)

Would the Lewis rule hold for the following binary

mixtures?
(1) C2H6 – CH3CN & (2) C2H6 – C3H8
3
 Lewis/Randall Rule
 ˆiid for fˆi id / xi P gives :

ˆiid  i
[148
 The fugacity coefficient of species i in an ideal
solution is equal to the fugacity coefficient of pure
species i in the same physical state as the solution
at the same T and P.

4
5
Activity coefficient
 lnγi is a partial property w.r.t. gE/RT and is
analogous to equation (69)
gE
  xi ln  i
RT i
Summability relations

 x d ln 
i
i i 0 (Constant T & P)

 Similarly:   ln  i  vi
E

  
 P  T , x RT

E
  ln  i  hi
   6

 T  P , x RT 2
Temp. & Pressure dependence of gE
 Fugacity defined at same temp. As reference state
 Useful to look at temp. Dependence of activity
coefficient via the excess Gibbs free energy
 For multi-component systems:
dgE = vEdP – sE + ∑giEdni

Differentiating w.r.p.t T & P leads to

 g E 
   v E  vmix and
 P T ,ni

 g E / T   h E  hmix
   2  7

 P  P ,ni T T2
 Two Suffix Margules Equation
Gibbs energy can be estimated by fitting experimental
results to analytical expressions for g E as with E.O.S.

Two Suffix Margules Equation provides a smple model

for expressing gE through γ with a limited amount of
experimental data, so for a binary solution

At xa = 1 and xb = 1 the solution is ideal so we must satisfy

two conditions:
 xa=1; xb = 0
The gE model satisfies the Gibbs-Dühem
 (1) g = 0
E (2) equation 8
 xb = 1; xa = 0
 Simplest nonideal model to satisfy both conditions:

 gE = Axaxb The two-suffix Margules equation

 Constant for given binary mixture that depends on temp.

& pressure but not composition

 This expression for gE allows the activity coefficients

to be determined via:

 gEa =Axb2 = RT lnγa and

 gEb =Axa2 = RT lnγb 9

 Temp. dependence of gE
 MDKEg7.12pp352: Enthalpy of mixing data for
C6H6(1)-C7H14(2) at 18.0oC has been fit to the
following expression: Δhmix=3250x1x2 [J/mol]. The
two suffix Margules parameter, A at 10.0 oC is
1401.0 [J/mol]. Estimate A at 60.0 oC and
compare it to data from the literature.

10
Heat Effects of Mixing

h  h   xi hi [139]

h  x1h1  x2 h2  h [140]

Heats of mixing similar to heats of reaction

but generally much smaller
11
Heats of Solution
 Effect of dissolving solid or gas in a liquid

~ h
h 
Heat of solution based on
one mole of solute.
[178]
x1

~
 LiCl(s) + 12H2O(l) -----LiCl(12H2O) h  33,614 J

 Eg: Calculate the heat of formation of LiCl in 12mol of

H2O at 25.0 oC
12
Solution
 Li + 1/2Cl2 ------------------- LiCl(s) Δho298=-408,610

~
 LiCl(s) + 12H2O(l) -------- LiCl(12H2O)
h298  33,614
~
 Li + /2Cl2(s) + 12H2O(l)-- LiCl(12H2O)
1 h298  442,224

Chemical change

Physical change

Net change is heat of solution

13
Typical data for heats of formation
 LiCl(s) -408,610 J
 LiCl.H2O(s) -712,580 J
 LiCl.2H2O(s)) -1,012,650 J
 LiCl.3H2O(s) -1,311,300 J
 LiCl in 3 mol H2O(s) -429,366 J
 LiCl in 5 mol H2O(s) -436,805 J
 LiCl in 8mol H2O(s) -440,529 J
 LiCl in10 mol H2O(s) -441,579 J
 LiCl in12 mol H2O(s) -442,224 J
 LiCl in15 mol H2O(s) -442,835 J 14
 Dissolution of 1 mol LiCl(s) in 5 mol H2O

 Li + 1/2Cl2 + 5H2O(l)-- LiCl(5H2O) Δho298=-436,805

 LiCl(s)-------- Li + 1/2Cl2 Δho298=408,610

 LiCl(s) + 5H2O(l) -------- LiCl(5H2O) Δho298=-28,195

 Dissolution of 1 mol LiCl.2H2O(s) in 8 mol H2O

 Li + 1/2Cl2 + 10 H2O(l)-- LiCl(10 H2O) Δho298=-441,579

 LiCl.2 H2O(s) -------- Li + 1/2Cl2 +2H2 + O2 Δho298=1,012,650
 2H2 + O2 ---- 2H2O(l) Δho298=(2)(-285,830)

 LiCl.2 H2O(s + 8H2O(l) -------- LiCl(10 H2O) Δho298=-589 15

Chemical Reaction Equilibria
 Analysis of chemical rxns important for
industrial production

 2 major components of analysis

 Kinetics – rates of rxn
 Equilibria – extent of rxn

 Extent tells how far a reaction will go

16
Extent of Rxn & Gibbs NRG
 At equilibrium G = Min [179]

 dG = 0 (const. T & P) [180]

 v1 A1+v2 A2 +…… vj Aj +vj+1 Aj+1 +….. [181]

17
 Reaction Coordinates
 At equilibrium G = Min Di-j Bond
dissociation
NRG (bond
H 2  Cl 2  2 HCl strenghts)

DH-H=4.5 eV
 HCl more stable (energetically favoured) DCl-Cl=2.5 eV
DH-Cl=4.5 eV

 For formation of 2 molecules of HCl the energy of the

molecules will be reduced by 2.0 eV
 Reversibility means 3 species in equilibrium
(entropically favoured)
18

 dG = 0 (const. T & P) [182]

 Extent of reaction

H 2  Cl2  2 HCl System initially has 1.0 mole Cl2

(species 2) and 1.0 Mole H2
(species 1) at a pressure of 1.0 bar
which react to form 2 mole HCl
(species 3)

n2  n1 [183]

[184]
n3  2(1  n1 )
Composition of any of the three species may be determined if
19
we know how far the reaction has gone (extent of reaction, ξ)
Extent of reaction
First identify the limiting

n1  1   reactant as the basis for the

extent of reaction [185]

If ξ is based on the H2 then

we can easily find how
much Cl2 has reacted

n2  1   [186]

n3  2 [187]
20
 Total Gibbs Energy
0   1 [188]

G   ni g i   ni  i  n1 1  n2  2  n3  3 [189]

pi
 i  g  RT ln
o
i [190]
1.0bar

21
 Gibbs Energy

G  n1 g10  n2 g 20  n3 g 30  RT (n1  n2  n3 ) ln P 

RT  n1 ln y1  n2 ln y2  n3 ln y3  [191]

term1

G  1    ( g10  g 20 )  g 30  2 RT ln P  RT  1    ln y1 

 (1   ) ln y2   ln y3 [192]

22
 Single reaction equilibrium
 The HCl reaction may be written as follows:
 A1 + A2 = 2A3 [193]

 A 1 = H2 A2 = Cl2 A3 = HCl [194]

 Re-aranging 0 = 2A3 - A1 - A2

stoichiometric coefficient:, 0 = v1A1 + v2A2 + v3A3

 v1= -1, v2 = -1, v3 = 2

23

Positive (+) for products and negative (-) for reactants

For the reaction: CH4 + H2O CO + 3H2

 vCh4=-1 vH2O=-1 vCO=1 vH2=3 [195]

 νreactants<0, νproducts>0, νinerts = 0

 For the reaction:

 C2H6 + 2H2O  2CO + 5H2 [196]

 v1= -1, v2 = -2, v3 = +2, v4 = +5

24
 ∑viAi = 0
 Change in reacting species
 Stoichiometric number for inert species are always zero.

 Change in mol numbers directly proportional to the

Stoichiometric number

 For 0.5 mol of CH4 consumed in the reaction 0.5 mol H2O
must also be consumed while 0.5 mol CO and 1.5 mol H2 are
formed

 The ratio of change in the number of moles of species 1 to

species 2 is given by:
25
 Reaction equilibrium

 change in moles  1 dn1 v1
  [197]
 change in moles  2 dn2 v2

dn1 dn2 dn1 v1 dn1 dn3

 similarly  or  [198]
v1 v2 dn3 v3 v1 v3

26
The Reaction coordinate
dn1 dn2 dn3
   .........  d [199]
v1 v2 v3

ni 
dni  vi d 
n0
dni  vi  d
0
[200]

[201]
ni  n10  vi

n
[202]
n 
v
i  n  v
0

vapour 27
Mole fraction and the reaction coordinate
 Mole fractions are related by:

ni ni0  vi
yi  v  0
n n  v [203]

1  1 
yH 2  , yCl2  and y HCl   [204]
2 2

28
 Example1
 Derive expressions for the mol fractions as a
function of ξ for the reaction:

 CH4+H2O →CO+3H2

 Assuming initial concentrations of 2.0 mol CH4,

1.0 mol H2O, 1.0 mol CO and 4.0 mol H2

29
Example2
 In a vessel containing n0 mol of water vapour
initially, decomposition occurs as follows:

 H2O→H2+1/2O2

 Express the number of moles of each

chemical species an a function of ξ

30
Example3
 What is the mol fraction of H2 produced in a
DMFC operating at 60.0 oC and low pressure
where the H2O doubles the CH3OH in the
feed if the extent of reaction at equilibrium is
0.87?

31
Multireaction stoichiometry
 The number of moles of species, ni may
change because of several reactions

 dni = ∑vi,jdξj (i=1,2,3…..N) [205]

 ni=nio+ ∑vi,jdξj (i=1,2,3…..N) [206]

 n=∑nio+∑i∑jvi,jξj=n0+∑j(∑i vi,j)ξj [207]

32
Multireaction
 n=n0+∑j vjξj [208]

n   vi , j j
0
i
j
yi  [209]
n   v j j
0

33
Example4.
 Determine expressions for yi in terms of ξ1 and ξ2
for the reactions:
 CH4+H2O →CO+3H2 (1)

 CH4+2H2O →CO2+4H2 (2)

 If initial compositions are:

 2.0 mol CH4& 3.0 mol H2O

34
Criteria for chemical equilibrium
 Gibbs energy change:

[210]
 dG=∑μidni=∑μiνidξ

dG
 0    i i [211]
d

ˆ
f
 i  g i0  RT ln i0 [212]
fi 35
 Substituting eq [215] into [211] gives:
 o fˆi 
0    g i  RT ln 0  i [213]

 f i 

i
fˆi     i i   rxn
   g 0
g 0
ln  [214]
 fi0  RT RT
 

g rxn
0
  i g i0 [215]
36
Equilibrium Constant

g rxn
0
ln K   [216]
RT

K  f (T only )
[217]

i
 fˆi 
 0   K
f 
 i  [218]
37
 K from thermochemical data

g rxn
0
, 298  g1  g 2    i  g 0f , 298  i   i f ,298 i  i f ,298 i
  g 0
    g 0 [219]
reac tan ts products

g rxn
0
 
  i g i0   i g 0f i [220]

Example
Calculate the equilibrium constant at 298K for the reaction:
H2O(g) + CH3OH(g) CO2(g) + 3H2(g)

38
 Temperature dependence of K

d ln K


d g / RT 0
rxn  [221]

dT dT

d ln K


g 0
rxn  1 dg 0
rxn

g 0
rxn

s
0
rxn
[222]
2 2
dT RT RT dT RT RT

Re call g 0
rxn  h0
rxn  Ts 0
rxn
[223]

39
K’s temp dependence


h
0
rxn i i
0

  h   i h 0

f i
[224]

h
0
rxn  const [225]

40
K’s temp dependence
 hrxn
0
 dT
d ln K    2
T [226]
 R 

K2 hrxn
0
1 1
ln     [227]
K1 R  T2 T1 

KT h  1
0
1 
ln   
rxn
 [228]
K 298 R  T 298 
41
Example
 Calculate the equilibrium constant at 60.0 oC
for the reaction:
 H2O(g) + CH3OH(g) CO2(g) + 3H2(g)

42
h o
rxn  h (T ) o
rxn
 For each reacting species
c 
p i
 Ai  BiT  CiT 2  DiT 2  EiT 3 [229]
R

T
  Di 3 
h o
rxn,T ,  ho
rxn, 298    R  i  Ai  BiT  CiT  2 * EiT  dT
2
[230]
298  i  T 

B 2 C 3
hrxn
o
,T   h o
rxn, 298  R

  A T  298  
2
 T  298  
3
 T  298 
3 

 
1  E 4
 D 
1
  T  2984   [231]
 T 298  4
43
 h o
rxn  h (T )
o
rxn
 Where:
A   i AI B   i B I C   i C i

D   i Di E   i Ei [232]

  h o
B C 3
d ln K
dT

rxn, 298
 A(T  298)   
T  298 
2
T  298 3 
 R 2 3
1  E 4  2
1
 D    
T  298  / T
4 [233]
 T 298  4  44
 h o
rxn  h (T )
o
rxn

 h o
B C
ln K T
K 298
  
rxn , 298

R

 A 298 
2
298 
2

3

2983 

D E 1 1 
   298    
298 4  T 298 
 T  B C 2
 A ln    T  298  T 
 298 2

 298  2 6
D  1 1  E 3
  2
2 T
 2 
 
T  298 3 
 
298  12 
[234]
45
Example5
 Find the room temperature, temperature
independent and temperature dependent
value of K for the reaction at 600.0oC:

 CH4O(g) = CH2O(g) + H2(g)

46
 AL FIN
 DONE

 KAPUT

 THE END

 ENDE

 A VÉGE

47