2023-2nd semester : Thermodynamics II

Thermodynamics II

5. 1st law of thermodynamics (2)

Jaekyoung Lee
Assistant professor
Chemical engineering
PKNU
Review

1st law of thermodynamics

ΔU = Uf − Ui = q + w
ΔU : the internal energy change
w : the work done on a system
q : the energy transferred as heat to a system

State function vs path function

2
Next

ΔU = Uf − Ui = q + w How to know work and heat?

3
Work
2A.3 expansion work
▪ Reversible vs Irreversible process

Reversible process : a process that can be reversed

by an infinitesimal modification of a variable.

dw = −|F|dz = −pAdz = −pdV

(-) : system do a work to the surrounding

Vf
w= ‫׬‬V −pdV
i

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Work

Expansion under constant pressure

Reversible isothermal expansion
Vf
w=
Vf
‫׬‬V −𝑝dV w = ‫׬‬V −𝑝dV reversible
i
i
V nRT
=−pexΔV = ‫׬‬V f − dV Perfect gas
i V
V 1 𝑉𝑓
= −nRT ‫׬‬V f dV = −𝑛𝑅𝑇 𝑙𝑛( ) isothermal
i V
𝑉𝑖
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Work

Expansion under constant pressure

Reversible isothermal expansion
Vf
w=
Vf
‫׬‬V −𝑝dV w = ‫׬‬V −𝑝dV reversible
i
i
V nRT
=−pexΔV = ‫׬‬V f − dV Perfect gas
i V
V 1 𝑉𝑓
= −nRT ‫׬‬V f dV = −𝑛𝑅𝑇 𝑙𝑛( ) isothermal
i V
𝑉𝑖
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Work

Expansion under constant pressure

Reversible isothermal expansion
Vf
w=
Vf
‫׬‬V −𝑝dV w = ‫׬‬V −𝑝dV reversible
i
i
V nRT
=−pexΔV = ‫׬‬V f − dV Perfect gas
i V
V 1 𝑉𝑓
= −nRT ‫׬‬V f dV = −𝑛𝑅𝑇 𝑙𝑛( ) isothermal
i V
𝑉𝑖
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Ex) Work
An external force holds the piston against an initial gas pressure of 14 bar. The external force on the piston is reduced
gradually, and the gas expands isothermally from the initial gas volume of 0.03 m3 to its double volume. If the volume
of the gas is related to its pressure so that PV is constant, what is the work done by the gas in moving the external
force?

How much work would be done if the external force were suddenly reduced to half its initial value instead of being
gradually reduced?

1. Situation

2. Idea

3. Calculation

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Ex) Work
An external force holds the piston against an initial gas pressure of 14 bar. The external force on the piston is reduced
gradually, and the gas expands isothermally from the initial gas volume of 0.03 m3 to its double volume. If the volume
of the gas is related to its pressure so that PV is constant, what is the work done by the gas in moving the external
force?

How much work would be done if the external force were suddenly reduced to half its initial value instead of being
gradually reduced?

1. Situation
▪ Pi = 14 bar / Vi = 0.03 m3
▪ PV = constant
▪ Isothermal expansion / force is reduced gradually

2. Idea
▪ Pi = 14 bar / Vi = 0.03 m3 (R,T, n ?) - Equation of state
▪ PV = constant
▪ Isothermal expansion / force is reduced gradually Reversible isothermal expansion
V
w = ‫׬‬V f −𝑝dV
i

9
Ex) Work
An external force holds the piston against an initial gas pressure of 14 bar. The external force on the piston is reduced
gradually, and the gas expands isothermally from the initial gas volume of 0.03 m3 to its double volume. If the volume
of the gas is related to its pressure so that PV is constant, what is the work done by the gas in moving the external
force?

How much work would be done if the external force were suddenly reduced to half its initial value instead of being
gradually reduced?

3. Calculation
Reversible isothermal expansion [Calculation] Unit J vs pressure
V 1 J = 1 N * m = 1 Pa * m3
w = ‫׬‬V f −𝑝dV PV = A
i

V 𝐴 𝑉
= − ‫׬‬V f dV = −𝐴 𝑙𝑛( 𝑉𝑓) = −𝐴 𝑙𝑛(2) = −𝑃𝑖𝑉𝑖 𝑙𝑛(2)
i 𝑉 𝑖

Calculation of A = −14 bar ∗ 0.03 m3 * ln(2)

= −14 bar ∗ 0.03 m3 *

100 𝑘𝑃𝑎 1𝐽
* ln(2) *
1 𝑏𝑎𝑟 1 𝑃𝑎 ∗𝑚3

= − 3.0 x 10 kJ
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Ex) Work
An external force holds the piston against an initial gas pressure of 14 bar. The external force on the piston is reduced
gradually, and the gas expands isothermally from the initial gas volume of 0.03 m3 to its double volume. If the volume
of the gas is related to its pressure so that PV is constant, what is the work done by the gas in moving the external
force?

How much work would be done if the external force were suddenly reduced to half its initial value instead of being
gradually reduced?

3. Calculation
Irreversible expansion

w =−pex (Vf−Vi) =−7 bar ∗ 0.03 m3 PV = A

100 kPa 1J
=−7 bar ∗ ∗ 0.03 m3 ∗
1 bar 1 Pa ∗m3

= −2.0 x 10 kJ

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Summary

ΔU = Uf − Ui = q + w How to know work and heat?

Vf
w= ‫׬‬V −pdV Reversible expansion
i

12
Situation – constant volume
2A.4 Heat transaction
dU = dq + dw Constant volume dU = dq𝑣 = Cv dT
𝑓 𝑓 𝑇𝑓
‫ 𝑖׬‬dU = ‫ 𝑖׬‬dqv = ‫ 𝑇׬‬Cv dT
𝑖

∆𝑈 = 𝑞𝑣 = Cv ∆T

1) The energy transferred as heat at constant volume = the change in internal energy of the system.

2) The heat capacity at constant volume (Cv) is defined as

Extensive properties

Molar heat capacity at constant volume, CV,m = CV/n,

Intensive properties
Specific heat capacity CV,s = CV/m.

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Situation – constant pressure
2B.1 Heat transaction
dU = dq + dw Constant pressure dqp = dU - dw
Enthalpy H = U + PV
= dU + pdV
State function
= d (U + PV)
=dH = Cp dT
∆𝐻 = 𝑞𝑝 = C𝑝 ∆𝑇

1) the energy supplied as heat at constant pressure

= the change in enthalpy

2)

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Heat capacity - Partial derivative

𝝏𝒚
Q. What is 𝝏𝒙 ?

A partial derivative of a function of more than one variable, such as f(x,y),

is the slope of the function with respect to one of the variables, all the other
variables being held constant

The chemist’s toolkit 9 Partial derivatives, p44, Physical Chemistry (Atkins) 15

Heat capacity

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Summary

ΔU = Uf − Ui = q + w How to know work and heat?

Vf
w= ‫׬‬V −pdV Reversible expansion
i

Constant volume (w = 0)

∆𝑈 = 𝑞𝑣 = Cv ∆𝑇

Constant pressure (w ≠ 0)

∆𝐻 = 𝑞𝑝 = C𝑝∆𝑇

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How to get the enthalpy from heat capacity?
Constant pressure
𝑓 𝑓 𝑇
‫ 𝑖׬‬dH = ‫ 𝑖׬‬dq𝑝 = ‫ 𝑓 𝑇׬‬Cp dT
𝑖
Does heat capacity depend on T? Molar internal energy molar heat capacity

∆H = 𝑞𝑝 No = Cp ∆𝑇 ∆Hm = Cp 𝑚 ∆𝑇
,
𝑇𝑓
Yes = ‫ 𝑇׬‬Cp dT 𝑇
𝑖
= ‫ 𝑓 𝑇׬‬Cp, 𝑚 dT
𝑖

Approximation (empirical)

2B.2(a), p49, Physical Chemistry (Atkins) 18

How to get the enthalpy from heat capacity?
Ex) What is the change in molar enthalpy of N2 when it is heated from 25 °C to 100 °C?
Use the heat capacity information in Table 2B.1.

1. Situation

2. Idea

3. Calculation

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How to get the enthalpy from heat capacity?
Ex) What is the change in molar enthalpy of N2 when it is heated from 25 °C to 100 °C?
Use the heat capacity information in Table 2B.1.

1. Situation

▪ ∆Hm (25 → 100 oC)

2. Idea
▪ T changes -> heat capacity depends on T
▪ Enthalpy vs temperature change

𝑇𝑓
∆H = ‫ 𝑇׬‬Cp dT 𝑇𝑓 C p
𝑖
∆H/n = ‫ 𝑇׬‬n 𝑑T
𝑖
𝑇
∆Hm = ‫ 𝑓 𝑇׬‬Cp, m 𝑑T
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𝑖
How to get the enthalpy from heat capacity?
Ex) What is the change in molar enthalpy of N2 when it is heated from 25 °C to 100 °C?
Use the heat capacity information in Table 2B.1.

[Calculation - Integration]

3. Calculation
𝑇𝑓
∆Hm = ‫ 𝑇׬‬Cp, m 𝑑T
𝑖

[Comment]

= 2.2 kJ mol−1

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Heat capacity changes with temperature under constant pressure (N2)

Cp , 𝒎

https://webbook.nist.gov/cgi/cbook.cgi?ID=C7727379&Units=SI&Mask=1&Type=JANAFG&Plot=on 22
Review

ΔU = Uf − Ui = q + w How to know work and heat?

Vf
w= ‫׬‬V −pdV Reversible expansion
i

Constant volume (w = 0)
𝑇
∆𝑈 = 𝑞𝑣 = Cv ∆𝑇 = ‫ 𝑓 𝑇׬‬Cv dT
𝑖

How is the relationship ?

- U vs H (Cv vs Cp)
Constant pressure (w ≠ 0)
𝑇𝑓
∆𝐻 = 𝑞𝑝 = C𝑝∆𝑇 = ‫ 𝑇׬‬Cp dT
𝑖

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Internal Energy U vs Enthalpy H
Enthalpy H = U + PV
∆H = ∆ U + P ∆ V Constant pressure)
≈∆U Solid, liquids)

2B.1(b), p47, Physical Chemistry (Atkins) 24

Internal Energy U vs Enthalpy H
Enthalpy H = U + PV
= U + nRT (Perfect gas)
∆H = ∆ U + ∆ ng RT (isothermal)
Ex) 2H2(g) + O2(g) → 2 H2O(l) at 298 K.
Calculate the difference between the molar enthalpy and internal energy changes in terms of 1 mol of O2 (g)

∆H-∆U = ∆ ng RT

= (-3 mol) * 8.314 J/mol K * 298 K

= -7.5 kJ

2B.1(b), p48, Physical Chemistry (Atkins) 25

Heat capacities Cp vs Cv

Constant pressure Perfect gas

dqp 𝜕T 𝜕V
Cp= = Cv ( )P +P ( )P
dT 𝜕T 𝜕T

𝜕V
dU = dq + dw = Cv + P ( )P V = nRT/P
𝜕T

dq = dU - dw = Cv + PnR/P
= dU + PdV
= Cv + nR
= CvdT + PdV

Cp-Cv = nR

2B.2(b) Physical Chemistry (Atkins) 26

Summary

ΔU = Uf − Ui = q + w How to know work and heat?

Vf
w= ‫׬‬V −pdV Reversible expansion
i

Constant volume (w = 0)

∆𝑈 = 𝑞𝑣 = Cv ∆𝑇

How is the relationship ?

- U vs H (Cv vs Cp)
Constant pressure (w ≠ 0)

∆𝐻 = 𝑞𝑝 = C𝑝∆𝑇
∆H = ∆ U + ∆ ng RT
Cp-Cv = nR
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Contents

ΔU = Uf − Ui = q + w How to know work and heat?

Vf
w= ‫׬‬V −pdV Reversible expansion
i

Constant volume (w = 0) How is the relationship ?

- U vs H (Cv vs Cp)
∆𝑈 = 𝑞𝑣 = Cv ∆𝑇
∆H = ∆ U + ∆ ng RT
Constant pressure (w ≠ 0)
Cp-Cv = nR
∆𝐻 = 𝑞𝑝 = C𝑝∆𝑇

Constant temperature

Adiabatic process

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