CHAPTER 2: 1ST LAW OF THERMODYNAMIC

Chapter 2 - Content
2.1 P-V work
2.2 Heat
2.3 1st law
2.4 Enthalpy
2.5 Heat capacity
2.6 Ideal gas & 1st law
2.7 Quantities calculation of 1st law

2.1 Work – force exerted on a body so as to move it from point

x1 to x2 at distance x is defined as,

x2 w F x cos
w F ( x)dx F x
x1

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2.1 PV work (Continue ..)

Problem example:
A woman lifts 30.0kg object slowly to a 2.00m height from its
original position. Calculate the work done by the woman.

Solution:
x2 Compare with work by
w F ( x)dx F x 1. Pushing horizontally
x1 2. Lifting at 30o angle
(mg)( x)
Compare 380,00 J/banana
2
(30.0 kg 9.81 m.s )(2.00 m)
588 J

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2.1 PV work (Continue ..)
A
surrounding P
x system

PV work (reversible) – pressure exerted on a body so that its

volume reduces by - V (A - x) is defined as,

2
wrev P(T , V )dV P V
1

Piston contraction = surrounding does work on the system

PV work (monodirection), dwirrev = -PdV – dKpist

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2.1 PV work (Continue ..)
PV work of a system can be determined from graph P versus V.

P 1 P
1

2
2

V1
V V
V2
V1 V2

P
V2

V2
V1
V1

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2.1 PV work (Continue ..)

Problem example:
Calculate the reversible work (in J) illustrated by the previous
Figure if P1=3.00atm, V1=500cm3, P2=1.00atm and V2=2000cm3.

Solution (case 1):

Area under the curve
1 / 2(3.00 - 1.00atm)(2000 500)cm 3 (1.00atm)(2000 500)cm 3
(1500 1500)atm.cm 3 3000atm.cm 3
5 -2 3
3 1.01325 10 Nm 1 10-2 m 1J
3000atm.cm 3
1atm 1cm 1N.m
304J

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2.1 PV work (Continue ..)

Solution (case 2):

Area under the curve

(3.00atm)(2000 500)cm 3
4500atm.cm 3
5 -2 -2 3
1.01325 10 Nm
3 1 10 m 1J
4500atm.cm 3
1atm 1cm 1N.m
456J

Is work a state function? Does it depend on the process path?

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2.2 Heat
Heat generated due to temperature difference can be computed
from the following equation,
T2

qP m cP (T )dT …(2.2a)
T1

where, cP is heat capacity

At constant pressure,
dqP H
CP
dT T P

At constant volume,
dqV U
CV
dT T V

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 2.3 1st Law of Thermodynamic http://lorien.ncl.ac.uk/ming/Webnotes/Therm1/1stLaw/onelt.htm

E=K+V+U
If kinetic energy, K and potential
energy, V do not influence the system, Open system
then total energy, E = internal energy, H=q+w
U.
Closed system
E=U U=q+w

Problem example:
Calculate U (cal) for 1 mole H2O experiencing change of
temperature from 25.0 to 30.0°C at 1.00atm. Water density at
25.0°C and 30.0°C are 0.9970 g/cm3 and 0.9956 g/cm3,
respectively. Molecular weight and heat capacity for water are
18g/mol and 1.00cal/(g°C), respectively.
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2.3 1st Law of Thermodynamic (Continue ..)
Solution:
qP mcP T
18 g 1 mol H 2O 1.00 cal 30.0 25.0 C
90 cal.
mol gC
2
w P dV P1 V
1
m m 1 1
P1 P1m
2 1 2 1

1 1 cm 3
(1.00 atm)(18g)
0.9956 0.9970 g
5 -2 3
3 1.01325 10 Nm 1 10-2 m 1J 0.23901 cal
0.025 atm.cm 3
1atm 1cm 1N.m 1J
0.00061 cal.

U = q + w = 90 – (0.00061) cal 90 cal

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2.4 Enthalpy, H

H is energy defined as,

H U +PV
H = U + (PV)
For constant P, closed system, and from U=q+w
H = (qP + w) + (PV) = (qP + w) + P( V)
H = (qP + w) + (-w) = qP
qP = H

For constant V, closed system, and from U=q+w

U = qV + w = qV + 0
U = qV
qV = U

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2.5 Heat capacity, C
- difference in heat with respect to temperature change.

i. Heat capacity at constant pressure, CP

dqP H
CP
dT T P

ii. Heat capacity at constant volume, CV

dqV U
CV
dT T V ..(2.2b)

U V
CP CV P
V T T P ..(2.5)
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2.6 Ideal gas & 1st law

Ideal gas 1st law

PV = nRT U For ideal gas,

0 internal energy = c
V T at constant T

From equation 2.5

U V
CP CV P
V T T P

and for ideal gas where internal energy difference= 0

CP,m – CV,m = R

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2.6 Ideal gas & 1st law (Continue ..)
Problem example:
0.1 mole ideal gas is operated in a cyclic process illustrated by
the following figure

P/atm
2 3
3.00

1.00 1 4

1000 2000 V/cm3

Cv,m = 1.5R and heat capacity are independent of temperature.

Calculate U for each process.

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2.6 Ideal gas & 1st law (Continue ..)

Solution:
T1 = P1V1/(nR) = 122K, T2 = 366K, T3 = 732K, T4 = 244K.

Employing dU = CVdT
Path 1-2, dU = (0.1mol)(1.50)(8.314 J/mol.K)(366-122)K
= 304.2 J
Path 2-3, dU = (0.1mol)(1.50)(8.314 J/mol.K)(732-366)K
= 456.0 J *
Alternatively,
du dqP dw ncP T ( PdV )
0.1 2.5R 732 366 3atm 1000cm3
= 456.3 J *

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2.6 Ideal gas & 1st law (Continue ..)

Path 3-4, dU = (0.1mol)(1.50)(8.314 J/mol.K)(244-732)K

= -608.6 J

Path 4-1, dU = (0.1mol)(1.50)(8.314 J/mol.K)(122-244)K

= -152.1 J

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2.6.1 Reversible isothermal process

For reversible isothermal & ideal gas,

U q w 0, w q
2 2 2
nRT dV
w q PdV dV nRT
1 1 V 1 V
V1 P2
nRT ln nRT ln
V2 P1 ..(2.6)

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2.6.1 Reversible isothermal process (continue ..)
Problem example:
0.1 mol ideal gas (Cv,m = 1.50R) expands isothermally and
reversibly from 1.00 to 3.00L at 300K. Calculate q, w and ΔU.

http://lorien.ncl.ac.uk/ming/Webnotes/Therm1/revers/isothe.htm

Solution:
V1 J 1
w nRT ln (0.1mol) 8.314 300K ln 274J
V2 mol.K 3
q - w 274J, U 0

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2.6.2 Reversible adiabatic process

dU dq dw U = CV ( T) = w
CV dT ( RT / V )dV
2 2
CV R V2 V1
dT dV R ln R ln
1 T 1 V V1 V2
Assuming heat capacity is independent of temperature
T2 V1
CV ln R ln ..(s)
T1 V2

PV P2V2 CP
Using 1 1 and
T1 T2 CV

P1V1 P2V2
http://lorien.ncl.ac.uk/ming/Webnotes/Therm1/revers/adbtc.htm

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2.7 Quantities calculation of 1st law
Summary of quantity calculation of q, w, U, H
based on a process

a. Reversible phase change at constant T and P

q = latent heat (eq. 2.2 cannot be used. During phase change
water steam, temp. remains at 100 C)
w = - PV, H = q, U = q + w

b. Heating at constant pressure w/o phase change

q = eq. 2.2 = H
w = - PV, U = q + w

c. Heating at constant volume w/o change of phase

q = eq. 2.2b
w = 0, H = U +V( P), U = q

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2.7 Quantities calculation of 1st law (continue ..)

d. State change for ideal gas (temperature change)

q= U-w
2 2
T
w PdV nR dV
1 1 V
T2 T2
U CV (T )dT , H CP (T )dT
T1 T1

e. Reversible isothermal process for ideal gas

H= U=0
w = eq (2.6) , q = -w
f. Reversible adiabatic process for ideal gas
dq = 0, dw = U
H & U can be calculated using eq.(s) in d
g. Adiabatic expansion for ideal gas in vacuum (= isothermal expansion)
q=w= U= H=0 (= free expansion, w=0)
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