Expansion work: Example

Thermodynamics The reaction Zn(s) + 2 HCl(aq) ZnCl2 (aq) + H2 (g) starts with
0.5 mol of Zn in a cylinder with a friction-less moving piston.
The volume inside the cylinder prior to the reaction is 25 l. The
atmospheric pressure is 1 bar and the temperature is 25 ◦C.

2015-10-09 Revision 1 Calculate the irreversible work done by the system on the
surroundings in this reaction.
2 Calculate the reversible work done by the system on the
surroundings in this reaction.
Fundamentals and 1st law 3

4
Sketch both processes in a p − V-diagram.
Repeat the above three calculations/steps for an initial
volume of 250 ml and comment on your result.

Expansion work: Example Irreversible work Reversible work

1. In this reaction, 0.5 mol of gas phase products are formed.

2. Irreversible: w = −pex ∆V, so the initial volume does not matter as
we are only looking for a difference.
∆V = ∆nRT/ pex = 0.5 mol · 8.314 J·mol−1 ·K−1 · 298 K/ 1 × 105 Pa =
12.4 l = 1.24 × 10−2 m3 and therefore
w = −1 × 105 Pa · 1.24 × 10−2 m3 = −1.24 kJ
3. Reversible: Here the change is slow and ∆T = 0 (isothermal).
w = −1.5 mol · 8.314 J·mol−1 ·K−1 · 298 K · ln(37.4 l/ 25 l) = −1.5 kJ
4. Lower starting volume, irreversible: no difference, only ∆V.
5. Lower starting volume, reversible:
w = −1.5 mol · 8.314 J·mol−1 ·K−1 · 298 K · ln(12.65 l/ 0.25 l) = −14.6 kJ.
Pressure inside is much bigger due to the smaller volume.

p reversible

irreversible

pex

0.25l 12.65l 25l 37.4l ©HERIOT-WATT UNIVERSITY

B18AP April 2016 v3
 Heat and heat capacity
Thermodynamics Heat
Heat can be supplied by a chemical reaction, combustion or an
electrical heater such as a kettle, fan heater or hot plate.

2015-10-09 Revision q = Pt = IVt (5)

with the electrical power, P, the current, I, the voltage, V,

supplied over the time, t.

Fundamentals and 1st law Heat capacity

Consider the two different scenarios of heating air in a room or
water in a kettle. Both heaters have a power of 2.5 kW and are
on for 100 s therefore supplying the same heat of qV = 250 kJ.

Heat and heat capacity 1 The temperature of the air (V = 25 m3 ) would rise by
T = 12 ◦C. (Why does this seem too much?)
2 The temperature of 1.8 l of water in the boiler would rise by
T = 34 ◦C.
The different rise in temperature has its origin in a material
property, here the constant-volume heat capacity, CV .

∆U
qV = CV ∆T = ∆U with ∆V = 0 and CV = (6)
∆T

1. CV = qV / ∆T = 250 kJ/ 12 K = 20.83 kJ·K−1

2. Note that this is the heat capacity of the room and scales with the
amount of substance.
3. n = pV/ RT = 1000 mol so
CV,m = 20.83 kJ·K−1 / 1000 mol = 20.83 J·K−1 ·mol−1
4. Your room would not heat that quickly as it is not really a closed
system. The large heat capacity of the walls leads to large losses
in heating the air.
5. The same calculation needs to be carried out for water.
6. CV = qV / ∆T = 250 kJ/ 34 K = 7.35 kJ·K−1
7. n = m/ M = 100 mol so CV,m = 7.35 kJ·K−1 / 100 mol = 74 J·K−1 ·mol−1
8. Although the molar heat capacity of water is much larger than the
one for air, the temperature rise is larger here because of the
lower amount of substance.

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Heat capacity, CV , and internal energy, ∆U: example
Thermodynamics When 1.00 g of olive oil (mainly
C57 H104 O6 is burned in pure O2 in a
bomb calorimeter, the temperature of

2015-10-09 Revision the water bath increases from

22.000 ◦C to 22.241 ◦C. The heat
capacity of the calorimeter is
9.032 kJ·K−1 .

Fundamentals and 1st law 1

2
What is the heat produced by
burning 1.00 g of olive oil?
What is the change in internal
Bomb calorimeter
energy for the combustion of

Heat capacity, CV , and internal energy, ∆U: 1 mol of C57 H104 O6 ?

This example is taken from your first year lecture (Dr Valeria
Arrighi).

example

1. ∆U = w + q with ∆V = 0, so no work is done.

2. ∆U = q = CV (calorimeter)∆T = 9.032 kJ·K−1 · 0.241 K = 2.18 kJ
3. Here ∆U = q. We have calculated this for m = 1 g but need to
transfer this to 1 mol.
4. Molar weight of olive oil:
M = 57 · 12 g·mol−1 + 104 · 1 g·mol−1 + 6 · 16 g·mol−1 = 884 g·mol−1
5. ∆Um = ∆U · M/ m = 2.18 kJ · 884 g·mol−1 / 1 g = 1930 kJ·mol−1

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 State functions and heat capacity
Thermodynamics The internal energy U and the enthalpy H are state
functions (in contrast to path functions like w and q).

2015-10-09 Revision For a change in a state function only the initial and final
value need to be considered. The path taken is irrelevant.
Consequently dU and dH are exact differentials.

Fundamentals and 1st law

‚ Œ ‚ Œ
∂U ∂U
dU = dT + dV (10)
∂T V ∂V T
| {z }
CV

State functions and heat capacity

CV : Heat capacity at constant volume

‚ Œ ‚ Œ
∂H ∂H
dH = dT + dp (11)
∂T p ∂p T
| {z }
Cp

Cp : Heat capacity at constant pressure

1. The heat capacities Cp and CV for solids and liquids are almost
identical
2. Describe the connection between Cp and CV in the gas phase.
dH = dU + p dV
dH = dU + nR dT
‚ Œ ‚ Œ
∂H ∂U
= +nR
∂T p ∂T V
| {z } | {z }
Cp CV

Cp = CV + nR
Cp,m = CV,m + R

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 First law problem
Thermodynamics 1 mol of zinc is dissolved in aqueous hydrochloric acid at 298 K
and atmospheric pressure. The heat that is liberated is −151 kJ.

2015-10-09 Revision 1

2
Calculate the change in internal energy, ∆U.
How big is the change in enthalpy, ∆H?

Fundamentals and 1st law

First law problem

1. ∆U = w + q with q = −151 kJ.

2. How much work is done? Any expansion work w = −p∆V?
3. Zn(aq) + HCl(aq) ZnCl(aq) + 12 H2 (g)
4. ∆n = 0.5 mol so
w = −p∆V = −∆nRT = −0.5 mol·8.314 J·mol−1 ·K−1 ·298 K = −1.24 kJ
5. ∆Uw + q = −1.24 kJ − 151 kJ = −152.2 kJ
6. ∆H = ∆U + p∆V = qV = −151 kJ

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Enthalpy of phase transition: example
Thermodynamics Example: melting of ice
Calculate the enthalpy change for the melting of a 10 g ice
cube taken out of the freezer (Ti = −18 ◦C) and left on the

2015-10-09 Revision kitchen bench (Tf = 21 ◦C).

Cp,m (H2 O(s)) = 37 J·K−1 ·mol−1
Tfus = 273.15 K
∆fus H−
◦ = 6.01 kJ·mol−1

Fundamentals and 1st law Cp,m (H2 O(l)) = 75.3 J·K−1 ·mol−1

Enthalpy of phase transition: example

1. Construct a thermodynamical cycle based on reversible processes.

2. 1. Heat ice to fusion/melting temperature, 2. Fusion/melting of ice,
3. Heat water from fusion/melting temperature to final
temperature.
3. ∆H1 = Cp,m ∆T = 37 J·K−1 ·mol−1 · 18 K = 666 J·mol−1
4. ∆H2 = ∆fus H−◦ = 6.01 kJ·mol−1
5. ∆H3 = Cp,m ∆T = 75.3 J·K−1 ·mol−1 · 21 K = 1580 J·mol−1
6. ∆Hm = ∆H1 + ∆H2 + ∆H3 = 8.26 kJ·mol−1
7. m = 10 g and M = 18 g·mol−1 , so ∆H = ∆Hm · m/ M = 4.59 kJ

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Entropy change: heating
Thermodynamics From equation 9 we know:

2015-10-09 Entropy and 2nd law

dH dq
Cp = =
dT dT
dqrev Cp
dS = = dT
T T

Heating
Z Tf
Cp
∆S = dT
Ti T

If Cp is independent of temperature (usually only over a small

range):

Entropy change: heating ∆S = Cp ln

Tf
Ti
(16)

Example
You drink a glass of tap water (200 g, 10 ◦C). Assuming a body
temperature of 36 ◦C, what is the change in entropy?
(Cp,m = 75.5 J·K−1 ·mol−1 )

1.
m Tf
∆S = Cp,m ln
M Ti
200 g 309 K
= 75.5 J·K−1 ·mol−1 ln
18 g·mol−1 283 K
= 74 J·K−1

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Entropy change: expansion
Thermodynamics The energy transferred as heat to a perfect gas when it
undergoes reversible isothermal expansion is:

2015-10-09 Entropy and 2nd law

Z Vf Z Vf
nRT Vf
qrev = −w = p dV = dV = nRT ln
Vi Vi V Vi
For the change in entropy in this process follows:
Vf
Expansion ∆S = nR ln
Vi
(17)

Examples

Entropy change: expansion A sample of carbon dioxide that initially occupies 15.0 dm3
1

at 250 K and 1.00 atm is compressed isothermally. Into

what volume must the gas be compressed to reduce the
entropy by 10.0 J·K−1 ? (Atkins, 4.6)
2 A monoatomic perfect gas at a temperature Ti is expanded
isothermally to twice its initial volume. To what
temperature should it be cooled to restore its entropy to its
initial value? CV,m = 23 R. (Atkins, 4.11)

• Example 1: Rearrange equation 17 for Vf

Vf
∆S = nR ln
Vi
∆S Vf
= ln
nR Vi
‚ Œ
∆S Vf
exp =
nR Vi
‚ Œ
∆S
Vf = Vi exp
nR

• Calculate n based on the ideal gas law: n = pV/ (RT) =

100 000 Pa · 1.5 × 10−2 m3 / (8.314 J·mol−1 ·K−1 250 K) = 0.72 mol
• And then calculate Vf
−10.0 J·K−1
!
3
Vf = 15.0 dm exp = 2.8 dm3
0.72 mol8.314 J·mol−1 ·K−1
©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Entropy change: expansion
Thermodynamics The energy transferred as heat to a perfect gas when it
undergoes reversible isothermal expansion is:

2015-10-09 Entropy and 2nd law

Z Vf Z Vf
nRT Vf
qrev = −w = p dV = dV = nRT ln
Vi Vi V Vi
For the change in entropy in this process follows:
Vf
Expansion ∆S = nR ln
Vi
(17)

Examples

Entropy change: expansion A sample of carbon dioxide that initially occupies 15.0 dm3
1

at 250 K and 1.00 atm is compressed isothermally. Into

what volume must the gas be compressed to reduce the
entropy by 10.0 J·K−1 ? (Atkins, 4.6)
2 A monoatomic perfect gas at a temperature Ti is expanded
isothermally to twice its initial volume. To what
temperature should it be cooled to restore its entropy to its
initial value? CV,m = 23 R. (Atkins, 4.11)

• Example 2: We want to double the volume, Vf = 2Vi and then

decrease the temperature to keep the entropy constant. Note that
Cp,m = CV,m + R for an ideal gas.
Tf 2Vi
Cp,m ln + R ln =0
Ti Vi
5 Tf
R ln + R ln 2 = 0
2 Ti
‚ Œ5
Tf 2
ln + ln 2 = 0
Ti
‚ Œ5/ 2
Tf 1
ln = − ln 2 = ln
Ti 2
‚ Œ5/ 2
Tf 1
=
Ti 2
1 2/ 5
Tf = Ti
2
Tf ≈ 0.76Ti
©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Example: the freezing of supercooled water
Thermodynamics 1 Construct reversible thermodynamic cycle
2 Calculate entropy changes of individual changes.

2015-10-09 Entropy and 2nd law Calculate the entropy change of the system.
3

4 Calculate the entropy change of the surroundings and the

total entropy change (∆Stot > 0).

Irreversible change
Example: the freezing of supercooled water

• Draw a thermodynamic cycle according to the scheme below.

• ∆S1 : Heating of water from 263 K to 273 K
∆S1 = Cp,m ln(Tf / Ti = 75 J·mol−1 ·K−1 ln(273 K/ 263 K) =
2.8 J·mol−1 ·K−1
• ∆S2 : Freezing of water at 273 K
∆S2 = −∆fus S = −22 J·mol−1 ·K−1
• ∆S3 : Cooling of ice from 273 K to 263 K ∆S1 = Cp,m ln(Tf / Ti =
37 J·mol−1 ·K−1 ln(263 K/ 273 K) = −1.4 J·mol−1 ·K−1
• ∆Ssys = ∆S1 + ∆S2 + ∆S3 = −20.6 J·mol−1 ·K−1
• ∆Ssur = qsur / T = −q/ T = −∆H/ T when p is constant.
∆Ssur = −(−∆fus H)/ T = 6000 J·mol−1 / 273 K = 22 J·mol−1 ·K−1
• This process is irreversible, so ∆Stot = ∆Ssys + ∆Ssur > 0.
∆Stot = −20.6 J·mol−1 ·K−1 + 22 J·mol−1 ·K−1 = 1.4 J·mol−1 ·K−1
• The process is spontaneous as ∆Stot > 0.

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Standard reaction entropy and direction
Thermodynamics Standard reaction entropy, ∆Sr−◦
X X
∆Sr−
◦
= −
◦
νi ∆Sm,i (products) − −
◦
νj ∆Sm,j (reactants) (24)

2015-10-09 Entropy and 2nd law

i j

Example

Direction of change 2 H2 (g) + O2 (g)

Data at T = 298.15 K: Sm
−
−
2
◦ (O (g)) = 205 J·K−1 ·mol−1 , S−
2 H2 O(l)
◦ (H (g)) = 131 J·K−1 ·mol−1 ,
◦ (H O(l)) = 70 J·K−1 ·mol−1 and
Sm 2 m 2
∆r H = −572 kJ·mol−1

Standard reaction entropy and direction We know this reaction is spontaneous.

Calculate ∆Ssys .
Is it spontaneous?
Can we tell?
Calculate ∆Ssur .
Calculate ∆Stot .
Is it spontaneous?
Can we tell?

1. ∆Sm = 2 · Sm−◦ (H O(l)) − 2 · S−

◦ (H (g)) − S−
◦ (O (g)) =
2 m 2 m 2
2 × 70 − 2 × 1 31 − 205 J·K−1 ·mol−1 = −327 J·K−1 ·mol−1
2. We cannot judge spontaneity on ∆Ssys alone.
3. ∆Ssur = −∆r H/ T = −(−572 kJ·mol−1 )/ 298.15 K = 1920 J·K−1 ·mol−1
4. ∆Stot = −327 J·K−1 ·mol−1 + 1920 J·K−1 ·mol−1 = 1590 J·K−1 ·mol−1
5. ∆Stot is large and therefore the reaction, as we know, is
spontaneous.

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Examples: maximum work
Thermodynamics Example: maximum available work and Gibbs free
energy

2015-10-09 Free energy Calculate how much energy can be extracted as (a) heat and
(b) work when 1.0 mol of glucose is oxidised.

C6 H12 O6 (s) + 6 O2 (g) 6 CO2 (g) + 6 H2 O(l)

Gibbs free energy ∆r U −

◦ = −2808 kJ·mol−1 and ∆ S−
r
◦ = 259 J·K−1 ·mol−1

Example: maximum non-expansion work and Helmholtz

free energy
Calculate how much energy is available to sustain muscle and

Examples: maximum work nervous activity in the human body (T = 37 ◦C) from the
combustion of 1.0 mol of glucose molecules under standard
conditions.

• Example: maximum available work when the volume is not kept

constant
• Assume the reaction is not dependent on temperature.
• qp = ∆H = ∆r H−◦ = ∆r U−◦ + ∆nRT with ∆n = 0 the volume is
constant and it follows ∆r H−◦ = ∆r U−◦ = −2808 kJ·mol−1
• wmax,exp = ∆r G−◦ = ∆r H−◦ − T∆r S−◦ =
−2808 kJ·mol−1 − 298 K · 259.1 J·K−1 ·mol−1 = −2885 kJ·mol−1
• Note that the maximum available work is larger than the change in
internal energy. This is down to generating many small molecules
from one large molecule (increase in entropy) which is favourable.
Therefore, the system can draw energy from the surroundings for
this process.
• Example: maximum non-expansion work, the volume in the cell is
constant.
• wmax = ∆r A−◦ = ∆r U−◦ − T∆r S−◦ = −2888 kJ·mol−1
• Molar weight of glucose, M = 180 g·mol−1 which according to
nutritional tables has "697 cal" which of course are 697 kcal. With
1 kcal = 4.184 kJ we calculate the nutritional value of 1 mol of
glucose as 2916 kJ, in very good agreement with our calculation.
©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Gibbs free energy: pressure dependence
Thermodynamics Solid and liquid:

(Ideal) gas:
Gm (pf ) = Gm (pi ) + Vm (pf − pi )

Gm (pf ) = Gm (pi ) + RT ln
pf
pi

2015-10-09 Free energy

Gibbs free energy
Gibbs free energy: pressure dependence
Example
Calculate ∆Gm of liquid water and ice, in equilibrium at 0 ◦C,
when the pressure is increased from 1.0 bar to 100 bar. The
mass densities of the two phases at 0 ◦C are
ρ(liquid) = 0.9999 g·cm−3 and ρ(ice) = 0.9150 g·cm−3 .

• Consider the two phases and the initial and final pressures pi and
pf .

∆Gm (pf ) = Gm (liquid, pf ) − Gm (ice, pf )

= [Gm (liquid, pi ) + Vm (liquid)(pf − pi )] − [Gm (ice, pi ) + Vm (ice
= ∆Gm (pi ) + [Vm (liquid) − Vm (ice)](pf − pi )
‚ Œ
1 1
∆Gm (pf ) − ∆Gm (pi ) = M − (pf − pi )
ρ(liquid) ρ(ice)
∆Gm = −16.5 J·mol−1
• This is an excellent exercise in unit conversion and should be
discussed in the workshop / tutorial.

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 The temperature dependence of ∆μ
Thermodynamics Example
Calculate ∆μ of liquid water and ice, in equilibrium at 0 ◦C and
1 bar, when the temperature is increased to 1 ◦C. The molar
entropies of the two phases are Sm (liquid) = 70 J·K−1 ·mol−1 and

2015-10-09 Free energy Sm (ice) = 38 J·K−1 ·mol−1 .

Chemical potential
The temperature dependence of ∆μ

• Remember ∆μ = ∆Gm .
• Similar approach as in example above but based on the
temperature change and chemical potential.
∆μ(Tf ) = μ(liquid, Tf ) − μ(ice, Tf )
= [μ(liquid, Ti ) − Sm (liquid)(Tf − Ti )] − [μ(ice, Ti ) − Sm (ice)(Tf − Ti
= ∆μ(Ti ) − [Sm (liquid) − Sm (ice)](Tf − Ti )
∆μ(Tf ) − ∆μ(Ti ) = −[Sm (liquid) − Sm (ice)](Tf − Ti )
∆μ = −31.92 J·mol−1

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Phase boundaries
Thermodynamics At a phase transition the chemical potentials of two coexisting
phases are equal:

2015-10-09 Free energy

Phase boundaries
Phase boundaries

• Derive Clapeyron equation based on figure on previous slide.

μ(α; p, T) = μ(β; p, T)
dμ(α) = dμ(β)
With dμ = Vm dp − Sm dT :
Vm (α) dp − Sm (α) dT = Vm (β) dp − Sm (β) dT
(Sm (β) − Sm (α)) dT = (Vm (β) − Vm (α)) dp
∆trs S dT = ∆trs V dp
∆trs H
With ∆trs S =
∆T
• Clapeyron equation
∆trs H
∆p = ∆T
T∆trs V

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Example: solid-liquid boundary
Thermodynamics Liquid sodium is used as a coolant in some nuclear
reactors
The melting point of Na (M = 23.0 g·mol−1 ) is 97.8 ◦C at a

2015-10-09
pressure of 1.00 bar. The densities of solid and liquid Na at this
Free energy temperature are 0.968 g·cm−3 and 0.927 g·cm−3 , respectively.
The molar enthalpy of fusion is ∆fus H = 2.64 kJ·mol−1 .

Calculate the melting point of Na at a pressure of 100 bar.

Phase boundaries
Example: solid-liquid boundary

• Use Clapeyron equation:

∆p ∆fus H
=
∆T Tfus ∆Vfus
• We need to calculate the difference in molar volumes upon fusion:
23.0 g·mol−1 23.0 g·mol−1
∆Vfus = V(l)−V(s) = −3
− = 1.051 cm3 ·mol−1
0.927 g·cm 0.968 g·cm−3
• It follows:
∆p 2640 J·mol−1
= = 6.77 × 106 Pa·K−1
∆T 371 K · 1.051 × 10−6 m3 ·mol−1
• Therefore, the melting point changes by:
( 100 − 1) × 105 Pa
∆T = = 1.46 K
6.77 × 106 Pa·K−1
• The melting temperature of sodium at 100 bar is 99.3 ◦C.
• Although the melting temperature increases under pressure,
solidification in a nuclear reactor is not an issue even©HERIOT-WATT
under highUNIVERSITY
pressures. B18AP April 2016 v3
 The liquid-vapour boundary
Thermodynamics dp
=
∆vap H
Slope of solid-liquid boundary
dT T∆vap V

2015-10-09 Free energy Entropy of vaporization is positive.

Volume change upon vaporization is
large and positive.
dp/ dT > 0 but smaller than for the

Phase boundaries
solid-liquid boundary.

dp ∆vap H
= (ideal gas)
dT T(RT/ p)

The liquid-vapour boundary d ln p

dT
=
∆vap H
RT 2
(41)

Clausius-Clapeyron equation
‚ Œ
∆vap H 1 1
ln pf = ln pi + − (42)
R Ti Tf
Temperature dependence of the vapour pressure.

1. Need to show that dT/ dp is large and hence that the boiling point
is more responsive to pressure than the freezing temperature.
2. from equ. 21 to 22 use dx/ x = dln x
3. do integral for Clausius-Clapeyron equation:
Z ln p
∆vap H T dT
‚ Œ
∆vap H 1 1
Z
d ln p = 2
= − −
ln p∗ R T∗ T R T T∗
4. assumptions made here (ideal gas, ∆H = const. do not hold near
the critical temperature. Requires equation of state (real gases).

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Example: boiling point
Thermodynamics The normal boiling point of benzene is 80.1 ◦C and the enthalpy
of vaporization is ∆vap H = 30.8 kJ·mol−1 .

Calculate the boiling point of benzene at a pressure of 100 torr.

2015-10-09 Free energy

Phase boundaries
Example: boiling point

• You need to distinguish between normal and standard conditions:

– Normal conditions: p = 1 atm = 760 torr = 101 300 Pa
– Standard conditions: p = 1 bar = 1 × 105 Pa
• Therefore, using the Clausius-Clapeyron equation and solving for
Tf :
‚ Œ
pf ∆vap H 1 1
ln = −
pi R Ti Tf
!−1
1 R pf
Tf = − ln
Ti ∆vap H pi
!−1
1 8.314 J·mol−1 ·K−1 100 torr
Tf = − ln
353.25 K 30.8 × 103 J·mol−1 760 torr
Tf = 296.0 K = 22.9 ◦C
• Notice the large change in boiling temperature upon lowering the
pressure.

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Quiz: Chemical potential at a triple point
Thermodynamics Which one of the three diagrams correctly reflects the chemical
potential at a triple point?

2015-10-09 Free energy

Chemical potential

Chemical potential

Chemical potential
Phase boundaries
Temperature Temperature Temperature

Quiz: Chemical potential at a triple point What is ’wrong’ with the other ones?

(red is correct)
Show on drawn phase diagram how the chemical potential changes with
temperature at constant pressure.
In case (green) the plot is correct but reflects a pressure which does never
intersect with the triple point and crosses all three phases. (White) is wrong
as the entropy is always positive (dμ/ dT)p = −Sm

©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3
 Example: Calculating an equilibrium composition
Thermodynamics Example: Ammonia synthesis

p2NH

2015-10-09
3

Chemical equilibrium I Species, J

K=
pN2 p3H

N2
2
= 977

H2 NH3
Initial pJ / bar 1.00 3.00 0

Equilibrium constant Change / bar

Equilibrium pJ / bar
−ξ
1.00 − ξ
−3ξ
3.00 − 3ξ
+2ξ
2ξ

Example: Calculating an equilibrium composition

• Calculate extent of reaction based on equilibrium constant:

(2ξ)2
K = 977 =
(1 − ξ)(3 − 3ξ)3
È
27 4 2
27
977(1 − ξ) = ξ with A = 977
4 4
A(1 − ξ)2 = ξ
ξ
ξ2 − 2ξ − 1 − =0
A
‚ Œ
1
ξ2 + Bξ + 1 = 0 with B = − 2 +
A
• Solving the quadratic equation yields:
s
‚ Œ2
B B
ξ=− − 1 yields ξ = 0.895
2 2
• pNH3 = 1.8 bar and pN2 = 0.1 bar and pH2 = 0.32 bar. ©HERIOT-WATT UNIVERSITY
B18AP April 2016 v3