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Thermodynamics

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39 views7 pages

Thermodynamics

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blue hues
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Heat Capacities (in units of R)

Molecule Translational Rotational Vibrational Cv Cp


Monatomic 3/2 0 0 3/2 5/2
gas
Diatomic gas 3/2 1 1 7/2 9/2
CO2 3/2 1 4 13/2 15/2
H2O 3/2 3/2 3 6 7
NH3 3/2 3/2 6 9 10
CH4 3/2 3/2 9 12 13

Summary of Degrees of Freedom

Translational Rotational Vibrational


Linear 3 2 3N-5
Nonlinear 3 3 3N-6

ɤ = Cp/Cv where: ɤ = is the ratio of the molar heat capacities at constant


pressure and volume
Exercises

1.Two moles of hydrogen at standard conditions are compressed adiabatically to a volume of 10


liters.For hydrogen,γ = 1.41.From these data,it is desired to find final pressure and temperature of
the gas.The known and unknown quantities are:
Initial Final
P1 = 1 atm P2 = ?
V1 = 2(22.4) = 44.8 liters V2 = 10 liters
T1 = 273.1 K T2 = ?
n=2 n=2
γ = 1.41 γ = 1.41

Where:R = 0.08206 L.atm/mol.K


P2 = P1(V1/V2)γ = 8.3 atm
T2 = P2V2/nR = 505.5 K or 232.3 oC

2.(a)Find the work done when 2 moles of hydrogen expand isothermally from 15 to 50 liters
against a constant pressure of 1 atmosphere at 25oC. Given:1 L.atm = 24.217 cal
w=PΔV = 847.5 cal
(b)Calculate the work performed when 2 moles of hydrogen expand isothermally and reversibly
at 25oC from 15 to 50 liters. Given:R = 1.987 cal/mol.K = 1.99 cal/mol.K
w=nRT ln V2/V1 =2.3 nRT log V2/V1 =1428 cal

3.Rxn:C6H6(l) + 15/2 O2(g) = 6CO2(g) + 3H2O(l) ΔE25oC = -781,100 cal


Calculate the heat of reaction.Use R = 1.99 cal/mol.K
ΔH = ΔE + ΔnRT = 782,000 cal

Exercises

1.Calculate the entropy change involved in the isotherrmal expansion of 1 mole of gas against a
constant pressure of 1 atmosphere from a volume of one liter to a volume of 10 liters at 300 K.
Given:R = 1.987 cal/mol.K Ans.4.58 cal/K.mol or 4.58 eu/mol

2.Calculate the entropy change involved in the isothermal expansion of 1 mole of gas against a
constant pressure of 1 atmosphere from a volume of 1 liter to a volume of 10 liters at 300 K.
ΔS = 2.303 R log V2/V1 = 4.58 eu/mol

3.Find the increase in entropy suffered by 2 moles of hydrogen on being heated at constant
pressure from 300 K to 600 K.The heat capacity per mole of the gas is given by the equation:

H2(g):ΔS =∫ CpdT/T
Ans.10.47 eu

Change of Entropy in Perfect Gases

A.Variable T and V
ΔS = nCv lnT2/T1 + nR ln V2/V1

B.Variable T and P
ΔS = nCp lnT2/T1 - nR ln P2/P1

C.Constant Temperature
ΔS = -nR ln P2/P1= nR ln P1/P2

Exercises

1.Find ΔS for 5 moles of an ideal,monatomic gas which is being compressed by heating from a
pressure of 1 atmosphere at 0oC to 10 atmospheres at 25oC.
For monatomic gas,Cp = 5/2R;R = 1.987 cal/mol.K
Ans.ΔS = -20.69 cal/K/5 moles or -20.69 eu/5 moles
ENTROPY CHANGE IN PHYSICAL TRANSFORMATION FOR REVERSIBLE
CONDITIONS (I.E WHEN EQUILIBRIUM EXISTS BETWEEN THE TWO FORMS)

ΔS = ΔH/T

Example

1.Finding the entropy difference for the transition


H2O(l,1 atm) = H2O(g, 1 atm) ΔH373.2 K = 9710 cal/mol

Ans.26.03 eu/mol

ENTROPY CHANGE FOR NONEQUILIBRIUM AND IRREVERISBLE TRANSITIONS

Example

1.Consider the reversible but nonequilibrium process at 373.2 K:


H2O(l,1 atm) = H2O(g,0.1 atm) ΔH373.2 K = 9710 cal/mol
Calculate the total change in entropy
ΔS = ΔSvaporization + ΔSexpansion = ΔH/T + R ln P1/P2
Ans.30.61 eu/mol

Ex.Messerly and Aston have shown that at 1 atmosphere pressure methyl chloride is solid
between 0 K and 175.44 K,liquid between 175.44 K and 248.94 K,and gaseous thereafter,and that
the entropies accompanying the heating of the solid,liquid,and gas between the temperatures
indicated are
ΔG or ΔF =Free energy change
FREE ENERGY OF IDEAL SUBSTANCES

ΔF = nRT ln P2/P1

ΔF = nRT ln C2/C1

FUGACITY AND ACTIVITY CONCEPTS

F = Fo + RT ln f/Po
F = Fo + RT ln a
F = Fo + nRT ln a2/a1

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