Thermodynamics - Repetition

1
What is one mole?
METALLIC SYSTEM

1 mole Pb = 1 g atom Pb
= No atomer Pb
(No = Avogadros number)
= 6,02252 * 1023 atoms Pb.
A solution of Pb and Mg

The composition corresponds to PbMg2

1 mole solution. = No atoms

= No / 3 atoms Pb + 2 * No / 3 atoms Mg

1 mol PbMg2 = Pb1/3Mg2/3

_______________________________

1 mole CaO = No. molecules CaO

1 mole SiO2 = No. molecules SiO2
1 moel CaSiO3 = ?

No. / 2 molecules CaO + No. / 2 molecules SiO2

We count molecules, not atoms

 io  Gi : standard Gibbs energy for pure i.
Gm : integral molar Gibbs energy for solution.

i  G i : partial molar Gibbs energy for component i in sol.

G M G M : relative integral molar Gibbs energy for solution.

M
G GiM : relative partial molar Gibbs energy for solution.
i

G xs G E : integral molar excess Gibbs energy.

Gixs GiE : partial molar excess Gibbs energy.

 Intrinsic and extensive state properties

Intrinsic properties:
- Can be defined at every point in the system
- Not dependent on the size of the system
- Examples: temperatur, tryck.

Extensive Properties:
- Dependent on the size of the system
- Examples: volume, inner energy etc..
- Proportional to the size of the system, (molar units).
For gases:
PV = NRT
H = U + (NRT)

For an ideal gas:

H = U + NR(T)

H is dependent on only T

För an isothermal ( = constant temperature) chemical reaction:

H = U + RT (N)

Changing in H is dependent on changing in N.

Reaction Enthalpy
Under constant pressure , P
(U2 + P·V2) - (U1 + P·V1) = Q

H2 - H1 = QP (Constant pressure)

H är a state property.

QP is obtained experimentally!

(Exempel: Reactions heat, Latent Heat of melting)

Let us consider the reaction

A + B = C + D

HC + HD( = HProdukt ) - (HA + HB( = HReaktant)) = H= QP

= Reaction enthalpy.
 Entropy
According to Second Law of
Thermodynasmics

1. ENTROPY is a state Property

2.ENTROPY Changes for a reversible

process is zero
 Gibbs Energy
At Equilibrium:

dH - TdS = 0

We define a new function: G = H - TS = Gibbs energy

dG = dH - TdS - SdT dG > 0 reaction

impossible

dG = 0 Equilibrium

dG = dH - TdS dG < 0 reaction possible

 io  Gi : standard Gibbs energy for pure i.
Gm : integral molar Gibbs energy for solution.

i  G i : partial molar Gibbs energy for component i in sol.

G M G M : relative integral molar Gibbs energy for solution.

M
G GiM : relative partial molar Gibbs energy for solution.
i

G xs G E : integral molar excess Gibbs energy.

Gixs GiE : partial molar excess Gibbs energy.

G

solid (s)

P
liquid (l)

T


P
liquid
(l)

gas (g)

T
G

l
P

T
Gibbs energidiagram
SOME SIMPLE PHASE DIAGRAMS
ºG- T – DIAGRAM
Referenser:
1. H.J.T Ellingham
J. Soc. Chem. Ind. 63 (1944), sid 125.
2. H.H. Kellog
J. Metals, vol 2 (1950), sid 862
vol 3 (1951), sid 137.
3. F.D. Richardson and J.H.E. Jeffes
J. Iron and Steel inst., vol 171 (1952), sid. 165.
__________
M + O2 = MO2
Vid jämvikt
G = 0

G  G prod.  Greakt.

 oG  o G prod.  o Greakt.

(Obs! ºG: Gibbs energy at standard stated)

G oGMO2 oGM  GO2 ;  oG  oGMO2 oGM oGO2

 oG  G   oG  0  GO2 oGO2  R  T  ln pO2

 G, Jmol-1

2Cu2O
F
F

2FeO

ºG, (Jmol-1)

2 CO
2 ZnO
E
2/3 Al2O3

Temperatur
ºG = RTlnpO2, kilojoules
ºG, kJ/mole
 -TS -TS

G = H - TS

kJ/mol

G = H - TS

H H

Illustration of the effect of the magniude of ºH on the ºG – T

relationships for reactions of the type 2M(s) + O2(g) = 2MO(s).
ºG
ºG (iii)
ºG, kilojoules
ºG, kilojoules per mole O2
For the galvanic cell

Fe(S) , FeO(S) // O2- // NiO(S), Ni(S)

a) Write the cell reaction.

b)Use the ºG – T diagram and calculate the cell EMF at 1000
C

Assume that the oxides and the metals do not dissolve in each
other

Answer: b) 290 mV
ºG, kJ/mole O2
ºG

ºHm(XO2)
ºHm(X)
ºG = ºH – TºS
ºS = ºSprod. - ºSreak.

REACTION EFFECT ON THE SLOPE (= -ºS)

REACTANT ºS reactant  increases

a) melts ºS  more negative
b) vaporizes ºG  more positive
Slope  more positive
(-ºS)

PRODUCT ºS product  increases

a) smälter ºS  more positive
b) förångas ºG  more negative
Slope  more negative (-ºS)
G, kJ/mole O2
G, kJ/mole Cl2
-G, kcal/gmole of chlorine
-G, kcal/gmole of chlorine
What can you read from Ellingham diagram?

 G for a reaction at a temperature

 S för en reaction in d G
o

dT
a temp. range.

H för en reaktion vid en viss temperatur.

- H2 / H2O –ratio
- CO / CO2 – ratio
- pO2
CONCEPT OF ACTIVITY

Activity (def., G.N. Lewis, 1907)

i oi  R  T  ln ai

(Gi  oGi  RT ln ai)

i = Chem. Potential of species ”i” in solution = Gi

i = Chem. Potential of pure species i, = o
Gi

(i and i – considered at the same temperature T).

 INTEGRAL MOLAR GIBBS ENERGY FOR
THE SYSTEM A – B
(valid for both attractive and repulsive interactions between A – B)

Gm
o
GB
x A o G A  X B o GB
 GBM
o
GA -GM
 G AM
GB
GA Gm  x A  GA  xB  GB

0 0
A B
XB 
XA = 1 XA = 0
XB = 0 XB = 1
GA  X A  GA  X B  GB

The line X A  G A  X B  GB
o o

corresponds to a mechanica mixture of A and B atoms without

forming a solution; for example a mixture of sugar and sand.

G M  ( X A  G A  X B  G B )  ( X A o G A  X B o G B )
G M  X A  (G A  o G A )  X B  (G B  o G B )
 X A  G AM  X B  G BM
 RELATIVE INTEGRAL MOLAR GIBBS ENERGY
AND
INTEGRAL MOLAR EXCESS GIBBS ENERGY
GM

0 0
I
II
GXS III

-GXS

A XB  B
G XS  G M  G M (ideal)
I = Repulsive Forces between A and B.

II = No repulsive or attractive forces (ideal solution).

The curve II should be symmetrical RT  ( X A  ln X A  X B  ln X B )

III = Attractive forces between A and B.

(The curves I and III need not be symmetrical!)
 INTEGRAL AND PARTIAL MOLAR EXCESS
GIBBS ENERGY
GX
S

I GBXS vid X B'

G AXS vid X B' II
0
III
GBXS vid X B''
G AXS vid X B''

A X B' X B'' B
XB XB = 1
XA =

1
G XS  X A  G AXS  X B  GBXS

I =Repulsive forces between between A and B

II = No repulsive or attractive forces (ideal solution), GXS = 0

III = Attractive forces between A and B.

(The curves I and III need not be symmetrical!!)

Tangent rule (and corresponding equations) are applicable for

getting the respective partial molar properties
Tangent to (I) at X’B and to (III) at X’’B.
INTEGRAL AND PARTIAL MOLAR ENTHAPIES
(VALID EVEN FOR VOLUMES)
Hm
HB

I H BM
H II
H AM o
HB
HA M III
o
HA -
HM HB
HA

0
0 A X’B B
XA = 1 XB  XB = 1
Hm  X A  HA  XB  HB

H M  X A  ( H A  o H A )  X B  ( H B  o H B )  X A  H AM  X B  H BM

I = Repulsive forces between A and B.

II = No repulsive or attractive forces (ideal solution), s.

Hm  X A  HA  XB  HB  X A o H A  X B o H B

III = attractive forces between A and B

(The curves I and III need not bebsymmetrical!!)
Tangent rule (and the corresponding equations are applicable to get the
partial molar properties.
 INTEGRAL AND PARTIAL MOLAR EXCESS
ENTHALPIES (VALID EVEN FOR VOLUME)
HM

H BM
I
H AM HX
S II
0 0
III
 H AM -HXS  H BM

A X’B X’’B B
XA = 1 XB  XB = 1
H M  H XS , H AM  H AXS , H BM  H BXS

I = Repulsive forces between A and B

II = No repulsive or attractive forces (ideal solution), HM = 0

III = Attractiva forces between A and B.

(Curves I and III need not be symmetrical!)

Tangent rule and corresponding equations apply to get the partial molar
quantities.
 INTEGRAL AND PARTIAL MOLAR ENTROPIES
AND
RELATIVA INTEGRAL MOLAR ENTROPIS
Sm

S BM
S AM SM
o
SB
o
SA
SB
SA

0
A X’B B
XB 
S  X A  S A  X B  SB
Tangent at the composition X’B will lead to partial molar entropies.

Dashed line corresponds to X A o S A  X B o S B

Mechanical mixture of atoms without interactions

S M  X A (S A  o S A )  X B (S B  o S B )  X A  S AM  X B  S BM

Obs! Entropi increases always when two species dissolve in each other.
REL. INTEGRAL AND OCH REL. PARTIAL MOLAR ENTROPIES
AND INTEGRALA MOLAR EXCESS ENTROPIES
SM

I
-
SXS
II

0 0
A B
XB 
I = No repulsive or attractive forces (ideal solution), total disorder
(Curve I must be symmetrical and the corresponding eqn. .

S M   R  ( X A  ln X A  X B  ln X B )

II = Repulsive or eller attractive forces between A and B (more

order)
(Curve II need not bev symmetrical)

Tangent rule (and the corresponding equations) apply for getting

the partal molar properties

(OBS! Excess(positional)entropy must alway be vnegative)

Excess entropy can be plotted in thesame way.
GIBBS-DUHEM EKVATION
(Gaskell: sid. 224-226 )

At constant T och P

dB  X 1  dB1  B1  dX 1  X 2  dB2  B2  dX 2

X 1  dB1  X 2  dB2  0

X 1  dG1  X 2  dG2  0

eller för fler  komponent system :

kallas GIBBS-DUHEM EKVATION.

 X i  dG i  0
For calculsating the Distribution constant for the distribution
of small amounts of Ag between lead and zinc, the
thermodynamic data for the binaries Pb-Ag(1) och Zn-
Ag(1) are needed.
Pb-Ag is assumed to be regular in the molten phase and the
characteristic constant is 10800 J mol-1-
For the reaction
Ag(1), supercooled = Ag(Zn, 1) in wt %
∆G0 at 1000 K är 55444 J mol-1
Calculate the Nernst distribution constant for the distribution
of Ag between
Pb(1) and Zn(1) vid 1000K.
The mutual solubilities of Pb and Zn at 1000 K can be
neglected..