Thermodynamics of an Ideal Gas

Ideal Gas
The hypothetical condition approached by real gases at high temperatures and low pressures (PV = nRT) The average translational energy for one mole of gas at a given temperature in Kelvins
(KE)ave = 3 2 RT

Ideal Gas
The hypothetical condition approached by real gases at high temperatures and low pressures (PV = nRT) The average translational energy for one mole of gas at a given temperature in Kelvins
(KE)ave = 3 2 RT

Molar Heat Capacity ( C )

The energy required to raise the temperature of 1mole of a substance by 1K.

heat

q = n C DT
moles change in temperature

Molar Heat Capacity ( C )

The energy required to raise the temperature of 1mole of a substance by 1K.

heat

q = n C DT
moles change in temperature

J/mol K

Heating an Ideal Gas at constant volume

(KE)ave = 3 2 RT = 3 2 RT

(heat energy required)

No change in volume - no work done

Cv = 3 2 R
heat energy required to change the temp. of one mole of monoatomic gas 1 K at constant volume

Heating an Ideal Gas at constant pressure

the volume increases work is done
(heat energy required)

= +
(the energy needed to do the PV work)

(heat energy required to change the translation energy)

Heating an Ideal Gas at constant pressure

the volume increases work is done
(heat energy required) = 3 2 R + PDV PDV = nRDT For a 1 mole 1 K change Cp Cp = = 3 2 R +R +R =R
heat energy required to change the temp. of one mole of monoatomic gas 1 K at constant pressure

Cv

Heating a Polyatomic Gas

polyatomic gases absorb energy to excite rotational and vibrational motions in addition to translational motions causing higher Cv than (3/2)R Cp = Cv +R

Assuming ideal behavior if Cv is known Cp can be calculated for any gas

Heating a Gas and Energy

DE = 3 2 RDT for n moles DE = nCv DT

DE = Cv DT

At constant pressure work is done

(heat energy = required)

qp = nCpDT = n(Cv + R) DT

DE

PDV

DH = nCv DT + nR DT

Heating a Gas and Enthalpy

H = E + PV DH = DE + D (PV) DH = DE + nRDT DH = nCvDT + nRDT DH = n(Cv + R) DT DH = nCpDT

Summary
q = nC DT Cv = DE = nCv DT DH = nCpDT 3 2 R

Cp = Cv + R

Example: Heating an Ideal Gas

Consider 2.00 mol of a monoatomic ideal gas that is taken from state A (PA = 2atm, VA = 10L )to state B (PB = 1atm, VB = 30L) by two different pathways: calculate q, w, DE, and DH for the two pathways
(PA = 2atm, VA = 10L ) (PC = 2atm, VC = 30L)

Path 1

P(atm)
Path 2 (PD = 1atm, VD = 10L) (PB = 1atm, VB = 30L)

V(L)

VA = 10L VC = 30L PDV = nRDT

Step 1

A B
101.3 J 1atmL = 4.05 x 103 J

At constant pressure = 2atm PDV = (2atm) (20L) = 40 atm L x nRDT = 4.05 x 103 J DT = w = -PDV = -4.05 x qp = nCpDT = n
v

4.05 x 103 J nR DH = qp = 1.01 x 104 J 4.05 x 103 J

3 4

103 J

( 2 R )( nR ) = 1.01 x 10 J 4.05 x 10 J 3 DE = nC DT = n ( R )( ) = 6.08 x 10 J nR 2

3

PC = 2atm PB = 1atm At constant volume = 30L DPV = nRDT DT =

Step 2
DPV nR -30 atmL nR

A B

DT = =

(30L)(1atm - 2atm) nR

101.3 J 1atmL =

-3.04 x 103J nR

w = 0 (no change in volume) qv = nCvDT = n DE = qv DH = nCpDT = n

3 2

)(

-3.04 x 103 J nR

) = -4.56 x 10 J
3

5 R 2

)(

-3.04 x 103 J nR

) = -7.6 x 10 J
3

PC = 2atm PB = 1atm At constant volume = 10L DPV = nRDT DT =

Step 3
DPV nR -10 atmL nR

A B

DT = =

(10L)(1atm - 2atm) nR

101.3 J 1atmL =

-1.01 x 103J nR

w = 0 (no change in volume) qv = nCvDT = n DE = qv DH = nCpDT = n

3 2

)(

-1.01 x 103 J nR

) = -1.52 x 10 J
3

5 R 2

)(

-1.01 x 103 J nR

) = -5.08 x 10 J
3

VA = 10L VC = 30L PDV = nRDT

Step 4

A B
101.3 J 1atmL = 2.03 x 103 J

At constant pressure = 1atm PDV = (1atm) (20L) = 20 atm L x nRDT = 2.03 x 103 J DT = w = -PDV = -2.03 x 103J qp = nCpDT = n
v

2.03 x 103 J nR DH = qp = 5.08 x 103 J 2.03 x 103 J

3 3

( 2 R )( nR ) = 5.08 x 10 J 2.03 x 10 J 3 DE = nC DT = n ( R )( ) = 6.08 x 10 J nR 2

3

Pathway One

A B

w = w1 + w2 = -4.05 x 103 J +

q = q1 + q2 = -4.56 x 103 J + 1.01 x 104 J = 5.5 x 103J DE = q + w = 5.50 x 103J - 4.05 x 103 J = 1.50 x 103J

DH = DH1 + DH2 = 1.01 x 104 J + 7.6 x 103J = 2.50 x 103 J

Pathway Two

A B

w = w3 + w4 = 0 - 2.03 x 103 J q = q3 + q4 = -1.52 x 103 J + 5.08 x 104 J = 3.56 x 103J DE = q + w = 3.56 x 103J - 2.03 x 103 J = 1.5 x 103J

DH = DH3 + DH4 = 2.53 x 103 J + 5.08 x 103J = 2.55 x 103 J

(PA = 2atm, VA = 10L )

w q DE DH Path 1

= = = =

-4.05 x 103 J 5.5 x 103J 1.50 x 103J 2.50 x 103 J

P(atm)
Path 2 w = - 2.03 x 103 J q = 3.56 x 103J DE = 1.5 x 103J DH = 2.55 x 103 J (PB = 1atm, VB = 30L)

V(L)

A State Function
Does not depend on how the system arrived at its present state; only on the characteristics of the present state. Volume, Pressure, Temperature, DE, DH