Exercises

Exercise 4

• Calculate the final V2, the final temperature T2 and the work done
when one relaxes suddenly and adiabatically 10 liters of perfect gas,
originally at 0 ° C from 10 to one atmosphere. Cv,m = 5 cal/mol.
Solution
• 10 liters of perfect gas

Adiabatic irreversible expansion V2 = ?

V1 = 10 L T2 = ?
P1 = 10 atm P2 = 1 atm
T = 0°C = 273 K
T
T
Adiabatic expansion Q=0

ΔU = Q + W = W

ΔU for a perfect gas depends only on temperature

dU = Cv dT

𝑇
∆𝑈 = ‫ 𝑇׬‬2 𝐶𝑉 𝑑𝑇 = 𝐶𝑉 (𝑇2 − 𝑇1 ) for one mole
1

for n mole, we should multiply by n

∆𝑈 = 𝑛 𝐶𝑉 (𝑇2 − 𝑇1 )

2
Work = − ‫׬‬1 𝑃𝑑𝑉 = −𝑃2 (𝑉2 − 𝑉1 )
Since sudden and irreversible relaxation, therefore P is the final
pressure P2

𝑛𝑅𝑇2 𝑛𝑅𝑇1 𝑃2
𝑊= −𝑃2 − = 𝑛𝑅 𝑇1 − 𝑇2
𝑃2 𝑃1 𝑃1
So ΔU = W =>

𝑃2
𝑛 𝐶𝑉 𝑇2 − 𝑇1 = 𝑛𝑅 𝑇1 − 𝑇2
𝑃1

𝑃2
𝐶𝑉 𝑇2 + 𝑅𝑇2 = 𝑅𝑇1 + 𝐶𝑉 𝑇1
𝑃1

𝑃2 1
𝑅 + 𝐶𝑉 2× +5 273 × 52
𝑃1 10
𝑇2 = 𝑇1 = 273 × = = 202.8 𝐾
𝐶𝑉 + 𝑅 7 70

System cooling

Expansion  system provides work.

Calculate V2 : we have T2 and P2

𝑛𝑅𝑇2
𝑃2 𝑉2 = 𝑛𝑅𝑇2 => 𝑉2 = =
𝑃2

In the condition (1) :

𝑃1 𝑉1 𝑃1 𝑉1 𝑅𝑇2 𝑇2 𝑃1
𝑃1 𝑉1 = 𝑛𝑅𝑇1 => 𝑛 = d’où 𝑉2 = . = . 𝑉1
𝑅𝑇1 𝑅𝑇1 𝑃2 𝑇1 𝑃2

For the work: 𝑊 = 𝑑𝑈 = 𝑛𝐶𝑉 (𝑇2 − 𝑇1 )

we can write 𝑊 = −𝑃2 (𝑉2 − 𝑉1 )

In both cases we have negative work, the system provides work

Exercise 5

Calculate the maximum flame temperature when 2 moles of H2 are

burned in the theoretical air quantity at 100 ° C and 1 atm. We suppose
that the combustion is complete (∆H = -116012 cal.)
 Cp H2O = 8.22 + 0.15 * 10-3 T + 1.34 * 10-6 T2

 Cp N2 = 6.76 + 0.605 * 10-3 T + 0.13 * 10-6 T2

2H2 + O2  2H2O
This is an exothermic reaction because ΔH < 0

But this quantity is carried by the product, it is the temperature of the

flame

ΔH must be equal - ΔHr = +116012 cal

ΔHr + ΔH = 0 (adiabatic) so ΔH = +116012 cal

 𝑇2
ΔH for a physical transformation is : ∆𝐻 = ‫ 𝑇׬‬σ(𝑛𝐶𝑝 )𝑖 𝑑𝑇
1

෍(𝑛𝐶𝑝 )𝑖 = 2𝐶𝑝 𝐻2 𝑂 + 4𝐶𝑝 𝑁2 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2

𝑇2
Tj > 0 (physical transformation) ∆𝐻 = ‫𝑇׬‬ 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 𝑑𝑇
1

1 1
𝑑𝐻 = 𝐴 𝑇2 − 𝑇1 + 𝐵 𝑇2 − 𝑇1 + 𝐶 𝑇23 − 𝑇13
2 2
2 3

116012 = ⋯
We calculate T2 by successive approximation

First step : we neglect therms in T2 and T3, we obtain :

∆𝐻 = 116012 = 𝐴 𝑇2 − 𝑇1 =>
116012 + 𝐴𝑇1
𝑇2 =
𝐴
First approximated value of T2 = (T2)a
Second step : we replace T2 by the approximated value (T2)a in 𝑇22 and 𝑇23 .
1 1
∆𝐻 = 𝐴 𝑇2 − 𝑇1 + 𝐵 (𝑇2 )2𝑎 −𝑇12 + 𝐶 (𝑇2 )3𝑎 −𝑇13
2 2

We calculate T2
This is a second approximayed value more precise than the first one so we obtain
(T2)b

Third step : we replace (T2)b in 𝑇22 and 𝑇23

Exercise 8
When n-hexane is passed over a chromium catalyst at 500 ° C, benzene
is formed according to the following equation:
C6H14 (g) → C6H6 (g) + 4H2 ∆H°298 = 59.78 kcal/mol
Calculate ∆H°T for the reaction at 500°C.
Cp = a + bT + CT2 Cal/degree mole

Gaz a b.103 c.107

Benzene -0.283 77.936 -262.96

n-hexane 7.313 104.906 -383.97

H2 6.9496 -0.1999 4.808

Solution
∆𝐻𝑇0 =
𝑇
∆𝐻𝑇0 = 0
∆𝐻𝑇1 + ‫ 𝑇׬‬σ(𝑛𝐶𝑝 )𝑖 𝑑𝑇
1

෍ 𝑛𝐶𝑝𝑖 = 4𝐶𝑝 𝐻2 + 𝐶𝑝 𝐶6 𝐻6 − 𝐶𝑝 𝐶6 𝐻14

= 4 6.9496 − 0.1999 × 10−3 𝑇 + 4.8 × 10−7 𝑇 2

+(−0.283) + 77.936 × 10−3 𝑇 + 262.96 × 10−7 𝑇 2
−7.313 − 104.906 × 10−3 𝑇 + 383.97 × 10−7 𝑇 2
𝐴 + 𝐵𝑇 + 𝐶𝑇 2 cal/degre.mol

773
° °
∆𝐻773 = ∆𝐻298 + න 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 𝑑𝑇
298

°
1 1
∆𝐻773 = 59.78 + 𝐴 773 − 298 + 𝐵 773 − 298 + 𝐶 7733 − 2983
2 2
2 3
Exercise 11

Demonstrate that it is impossible for two reversible adiabatic curves on

a P, V diagram to intersect
Solution
We suppose that (1) and (2) intersect at A
We cut the 2 adiabatic by an isobar in B and C

𝛾 𝛾
A and C ϵ to (1) so we can write : 𝑃𝐶 𝑉𝐶 = 𝑃𝐴 𝑉𝐴

𝛾 𝛾 𝛾 𝛾
𝑃𝐵 𝑉𝐵
A and B ϵ to (2) : = 𝑃𝐴 𝑉𝐴 donc : 𝑃𝐶 𝑉𝐶
= 𝑃𝐵 𝑉𝐵
et comme PC =
PB => VC = VB
So it is necessary that B and C are the same points on the two
adiabatics
Exercise 12

One mole of perfect gas is heated at constant pressure from 25 ° C to

300 ° C. Calculate the entropy change ∆S if Cv,m = 3 / 2R.
Solution
3𝑅
P = cte ; 𝐶𝑉 = T = 25°C  200°C
2

𝑑𝑇 𝑑𝑃
Perfect gas 𝑑𝑆 = 𝐶𝑝 − 𝑅
𝑇 𝑃

𝑑𝑇
P = cte => dP = 0 𝑑𝑆 = 𝐶𝑝
𝑇

𝑇2
𝑑𝑇 𝑇2
∆𝑆 = න 𝐶𝑝 = 𝐶𝑝 𝐿𝑛
𝑇 𝑇1
𝑇1
 3𝑅 5𝑅
𝐶𝑝 − 𝐶𝑉 = 𝑅 => 𝐶𝑝 = 𝐶𝑉 + 𝑅 = +𝑅 =
2 2
5𝑅 𝑇2 5𝑅 573
∆𝑆 = 𝐿𝑛 = 𝐿𝑛 Unit of ΔS depend on R
2 𝑇1 2 298
Exercise 13

Calculate the increases in U, H, S, F and G when a perfect gas relaxes

isothermally from 1 to 100 dm3 at 25 ° C.
Solution
U, H, S, F, G

Perfect gas :
ΔU = 0 isothermal (U depend on T)
ΔH is only function of T (perfect gas) ΔH = 0
ΔS = ?
𝑑𝑇 𝑑𝑉
𝑑𝑆 = 𝐶𝑉 +𝑅
𝑇 𝑉
 𝑑𝑉 𝑉 𝑑𝑉 𝑉2
Isothermal so, 𝑑𝑆 = 𝑅 ∆𝑆 = ‫ 𝑉׬‬2 𝑅 = 𝑅 𝐿𝑛 = 2 𝐿𝑛 100
𝑉 1 𝑉 𝑉1

ΔS = 9.2 cal/K mol

F = U – TS => ΔF = ΔU – TΔS – SΔT

Isothermal : ΔU = 0 and ΔT = 0 => ΔF = – TΔS = -298 (9,2) = 2744,68
calorie/mol

G = H – TS => ΔG = ΔH – TΔS – SΔT

Isotherme : ΔH = 0 et ΔT = 0 => ΔG = – TΔS = -298 (9,2) = 2744,68
calorie/mol
Exercise 14

10 g of carbon monoxide at 0°C are reversibly and adiabatically

compressed from 1 to 20 atm. Calculate ∆U, ∆H, ∆S for this change. It is
assumed that Cv,m = 5 cal / ° C mol and that the perfect gas equation is
valid. Would it be possible to calculate ∆G from the data provided?
Solution
10 g of CO : T1 = 0°C ; P1 = 1 atm ; P2 = 20 atm CV = 5 cal/degre.mol
ΔU ; ΔH ; ΔS

For a perfect gas, ΔU is always f(T)

(1) ΔU = CV (T2 – T1)

Adiabatic transformation (gaz parfait)

1
−1
𝑇. 𝑃 𝛾 = 𝑐𝑡𝑒
1 1 1
−1 −1 𝑃1 (𝛾 −1)
𝛾 𝛾
𝑇1 . 𝑃1 = 𝑇2 . 𝑃2 => 𝑇2 = 𝑇1
𝑃2
 𝐶𝑝 𝐶𝑉 +𝑅 7
Or 𝛾 = = =
𝐶𝑉 𝐶𝑉 5

5 2
1 7
−1 1 −7
Alors 𝑇2 = 𝑇1 = 𝑇1 = 642.5 𝐾
20 20

2 2
−7 −7
1 1
∆𝑈 = 𝐶𝑉 𝑇1 −1 = 5 × 273 − 1 = 𝑥𝑥𝑥𝑥𝑥 𝑐𝑎𝑙/𝑚𝑜𝑙
20 20

10 10
The number of mol of CO is 𝑛 = => ∆𝑈 = 𝑥𝑥𝑥𝑥 × = 646.6 𝑐𝑎𝑙
28 28
 ∆𝑯 𝐶𝑝 7
(2) ΔH = Cp (T2 – T1) => = =
∆𝑼 𝐶𝑉 5

∆𝑯
We compare (1) and (2) and we find
∆𝑼

∆𝑆 = 0 (adiabatic)
𝐺 = 𝐻 − 𝑇𝑆 => ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 − 𝑆∆𝑇
∆𝐺 = ∆𝐻 − 𝑆∆𝑇

we have the values of ΔT and ΔH but we don′ t have that of S.

So we can’t calculate ΔG
Exercise 15
The following data relating to water are:
latent heat of vaporization, 9630 cal / mole;
latent heat of fusion, 1435 cal / mole;

molar specific heats:

 solid, Cp = 0.5 + 0.03T
 liquid, Cp = 18
 steam, Cp = 7.256 + 2.3.10-3 T + 2.83 * 10-7 T2

Calculate ∆S when 1 mole of water is heated from 100°K to 500°K under a

constant pressure of 1 atm.
Solution
ΔHv = 9630 cal/mole
ΔHf = 1435 cal/mole
Cp (solid) = 0.5 + 0.03 T
Cp (liquid) = 18
Cp (vapor) = 7.256 + 2.3 ×10-3 T + 2.83 ×10-7 T2

1 mole of water T1 = 100 K

T2 = 500 K P = cte = 1 atm

Initial state of water (solid) T1 = 100 K

Final state of water (vapor) T2 = 500K
We have : solide – liquid – vapor

Solid water (T1 = 100 K)-----∆𝑆1 ------solid water (273 K) heating

isothermal fusion

Solid water (273 K)-----(∆𝑆2 )------- liquid water (273K)

Liquid water (273K)-----∆𝑆3 --------liquid water (373 K) heating

isothermal vaporization
Liquid water (373 K) ----(∆𝑆4 )-------vapor water (373 K)

Vapor water (373 K) ----(∆𝑆5 )---------vapor water (373 K) heating

∆𝑆 = ∆𝑆1 + ∆𝑆2 + ∆𝑆3 + ∆𝑆4 + ∆𝑆5
273
𝑑𝑇
∆𝑆1 = න 𝐶𝑝
𝑇
100

273
𝑑𝑇 273
= න 0.5 + 0.03 𝑇 = 0.5𝐿𝑛 + 0.03 273 − 100
𝑇 100
100

= 5.69 𝑐𝑎𝑙/𝐾
ΔS2 change of phase at T = cte.

∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 1435 𝑐𝑎𝑙

∆𝑆2 𝑜𝑓 𝑓𝑢𝑠𝑖𝑜𝑛 = = = 5.25
𝑇𝑓𝑢𝑠𝑖𝑜𝑛 273 𝑚𝑜𝑙

373 373
𝑑𝑇 𝑑𝑇 373
∆𝑆3 = න 𝐶𝑝 𝑙𝑖𝑞𝑢𝑖𝑑 = න 18 × = 18 × 𝐿𝑛 = 5.61 𝑐𝑎𝑙/𝐾
𝑇 𝑇 273
273 273
 ∆𝐻𝑣𝑎𝑝 9630 𝑐𝑎𝑙
∆𝑆4 = = = 25.81
𝑇𝑣𝑎𝑝 370 𝐾

500

∆𝑆5 = ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟 = න 𝐶𝑝 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟

500 373
𝑑𝑇
= න (7.256 + 2.3 × 10−3 × 𝑇 + 2.83 × 10−7 × 𝑇2)
𝑇
373

500 1
= 7.256 𝐿𝑛 + 2.3 × 10 500 − 373 + × 2.83 × 10−7 5002 − 3732
−3
373 2

= 2.42 𝑐𝑎𝑙/𝐾
Exercise 19
Demonstrate that for a gas obeying the equation of state:
𝑃 + 𝑎ൗ 2 𝑉 − 𝑏 = 𝑅𝑇
𝑉

we have, for one mole of gas,

(𝜕𝑈/𝜕𝑉) 𝑇 = 𝑎ൗ 2
𝑉
Solution

𝑎 𝜕𝑈
𝑃+ 𝑉 − 𝑏 = 𝑅𝑇 N.B Fo𝑟 𝑎 𝑝𝑒𝑟𝑓𝑒𝑐𝑡 𝑔𝑎𝑠 =0
𝑉2 𝜕𝑉

𝜕𝑈 𝑎 𝜕𝑃 𝜕𝑉
) = ; 𝐿=𝑇 ; 𝑛 = −𝑇
𝜕𝑉 𝑇 𝑉2 𝜕𝑇 𝑉 𝜕𝑇 𝑃

𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

𝜕𝑈 𝜕𝑆
)𝑇 = 𝑇 −𝑃
𝜕𝑉 𝜕𝑉 𝑇

We know that 𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇

We know that 𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇

𝜕𝑆 𝜕𝑃
dF is an exact differential : donc on peut écrire : ) = )
𝜕𝑉 𝑇 𝜕𝑇 𝑉

𝝏𝑼 𝝏𝑷
) =𝑻 −𝑷
𝝏𝑽 𝑻 𝝏𝑻 𝑽

𝑅𝑇 𝑎
equation of state : 𝑃 = − 2
(𝑉−𝑏) 𝑉

𝜕𝑃 𝑅
)𝑉 =
𝜕𝑇 𝑉−𝑏
𝜕𝑈 𝑅 𝑇𝑅 𝑅𝑇
So = 𝑇. −𝑃 = −
𝜕𝑉 𝑇 𝑉−𝑏 𝑉−𝑏 𝑉−𝑏
Exercise 21
One mole of perfect gas undergoes the following reversible transformations:
a) Isothermal expansion from the initial state (10 atm, 2 liters) to the final state (5 atm)
b) Adiabatic expansion of this same initial state (10 atm, 2l) to a final state defined by a value
of the pressure equal to 5 atm.
1. Calculate (in cal) the values of Q, W, ∆U and ∆H during previous transformations a and b.
2. In a diagram showing the variations of P as a function of V, plot the paths followed by the gas in
each of these transformations.
3. There is a transformation (c) represented by a straight line in the P, V diagram, which is such
that all the transformations b and c bring the system into the same final state as that obtained
in a. What is the nature of this last process?

Given: Cv = 3 cal / mole

Solution
a) initial : P1 = 10 atm ; V1 = 2L
Isothermal expansion : P2 = 5 atm

Calculate Q ; W ; ΔU ; ΔH
a) Isothermal expansion, 1 mole of perfect gas
Isothermal expansion ΔU = ΔH = 0

𝑉 𝑉2
∆𝑈 = 𝑄 + 𝑊 = 0 => 𝑊 = −𝑄 = ‫ 𝑉׬‬2 −𝑃𝑑𝑉 = −𝑅 𝑇1 𝐿𝑛
1 𝑉1

𝑃1
𝑊 = −𝑄 = −𝑅 𝑇1 𝐿𝑛
𝑃2

𝑃1 𝑉1 𝑃1 𝑉1 10×2
𝑊 = −𝑄 = −2 𝐿𝑛2 𝑇1 = =
𝑅 𝑅 2

𝑊 = −𝑄 = −10 𝑎𝑡𝑚 × 2𝐿 × 0.69 => 𝑊 = −𝑄 = −13.8 𝐿. 𝑎𝑡𝑚

R = 2 cal/mol.K = 0.083 L.atm/mol.K

−13,8
𝑊 = −𝑄 = = −332.5 𝑐𝑎𝑙.
0.0415
b) Adiabatic expansion: Q = 0 ; CV = 3 cal

∆𝑈 = 𝑊 = 𝐶𝑉 (𝑇2 − 𝑇1 )
1 1 1
−1 −1 𝑃1 ( −1)
𝛾 𝛾 𝛾
Or 𝑇1 . 𝑃1 = 𝑇2 . 𝑃2
=> 𝑇2 = 𝑇1
𝑃2
𝐶𝑃 5
𝐶𝑃 = 𝐶𝑉 + 𝑅 = 5 𝑐𝑎𝑙 => 𝛾 = =
𝐶𝑉 3
2
−
𝑃1 5
𝑇2 = 𝑇1
𝑃2
 2
−
𝑃1 5 𝑃1 𝑉1 −2
∆𝑈 = 𝑊 = 𝐶𝑉 𝑇1 −1 = 𝐶𝑉 25 −1
𝑃2 𝑅

𝑃1 𝑉1 𝑃1 𝑉1
∆𝑈 = 𝐶𝑉 0.75 − 1 = −0.25 𝐶𝑉
𝑅 𝑅
3 −7.5
𝑊 = ∆𝑈 = −0.25 × × 10 × 2 = −7.5 𝐿. 𝑎𝑡𝑚 =
2 0.0415

= −180 𝑐𝑎𝑙
∆𝐻 = 𝐶𝑃 (𝑇2 − 𝑇1 )

∆𝑈 = 𝐶𝑉 (𝑇2 − 𝑇1 )

∆𝐻 5
= 𝛾 => ∆𝐻 = 𝛾. ∆𝑈 = −180 = −300 𝑐𝑎𝑙
∆𝑈 3
2
𝑃1 −5
𝑇2 = 𝑇1 = 𝑇1 (0.75) donc T2 < T1
𝑃2

from the slopes I know the adiabatic curve