FYI

from textbook…
Increase temperature -> distribute atoms to higher energy levels (heat capacity: ability of atoms/molecules to
redistribute themselves amongst different energy levels to accommodate difference in energy)

Some Examples
An ideal gas undergoes a transformation from n=1.75mol, P=2.50bar, T=335k to n=1.75mol, P=0.225bar in a
number of ways. For each find q, w, delta u + delta H.

Heat capacity for ideal gas
Cv = 3/2R
Cp = Cv + R = 5/2 R

a) Isothermally + irreversibly against a constant external pressure Pext = 0.225
Because isothermal, T1 = T2 = 335 ∆𝑇 = 0 and also ∆𝑈 = ∆𝐻 = 0
P1 = 2.5bar -> P2 = 0.225bar
∆𝑈 = 𝑞 + 𝑤 → 𝑞 = −𝑤
W = −𝑃-./ ∆𝑉 (we don’t need to integrate because constant pressure) now we need to figure out
∆𝑉
123 123 (5.89:;<)(>.>?@5A)(@@9B)
𝑉= -> 𝑉5 = = = 19.5𝐿
4 4 C.9>DEF
-1 -1
Where R = 0.083144621 L bar K mol
123 (5.89:;<)(>.>?@5A)(@@9B)
𝑉C = =
4K C.9>DEF
V2 = nRT/P2 = 217L
W = -Pext(V2 – V1) = -(0.225bar)(198L)
Logic: Gas is expanding. Pushing surrounding back. System doing work on system ->energy
leaving system. Work should be negative.
q = -w
It is absorbing the equivalent amount of work.
b) Adiabatically + irreversibly against a constant external pressure Pext = 0.225
Cannot absorb energy so q = 0, irreversibly means constant external pressure (can be several stages
but can break them up into separate steps with constant values)
P1 = 2.50bar P2 = 0.225bar
T1 = 335k T2 = ?
If q = 0 then ∆𝑈= w =𝑛𝐶𝑣∆𝑇=−𝑃-./ ∆𝑉
123P
𝑉𝑖 =
4P
123Q 123R
𝑤 = −𝑃-./ − two unknowns, w and Tf, replace w with 𝑛𝐶𝑣∆𝑇 since we know n and Cv
4Q 4R

3Q 3R
−𝑃-./ 𝑛𝑅 − = 𝑛𝐶𝑣(𝑇U − 𝑇𝑖)
4Q 4R
124VWX 124VWX
𝑇C 𝑛𝐶𝑣 + = 𝑇5 (𝑛𝐶𝑣 + ) T2 = 213K
4K 4Y

∆𝑈 = 𝑛𝐶𝑣 𝑇U − 𝑇𝑖 = 1.75𝑚𝑜𝑙 3/2(8.314)(213𝐾 − 335𝐾) = -2.66x10^3J
(R is J/kmol)
negative U is expected because energy is lost from system because of work done
9
∆𝐻 = 𝑛𝐶𝑝 𝑇U − 𝑇𝑖 = 𝑛 𝑅 𝑇U − 𝑇𝑖 = −4.44𝑥10^2𝐽
C


 c) Isothermally + reversibly to Pf = 0.225 bar
Isothermal means delta T = 0, ∆𝑈 = ∆𝐻 = 0, q = -w,
Reversible: don’t have constant external pressure (internal/external pressure are always in
equillibium and brought down slowly Pint = Pext
P = nRT/V -> replace P in work definition
iC 123
𝑤 = − i5 𝑃-./ 𝑑𝑉 = − 𝑑𝑉 = 𝑛𝑅𝑇 ∗ 𝑙𝑛𝑉
i
V1 = 19.9L and V2 = 217L (calculated in a)
iC
𝑤 = −𝑛𝑅𝑇 ln = −11.7𝑥10^3𝐽
i5
expansion so we expect work to be negative
q = -w = 11.7x10^3J

d) Adiabatically + reversibly to Pf = 0.225 bar
q = 0 and T will change, reversible = continuous (so we need to integrate)
∆𝑈 = 𝑛𝐶𝑣 𝑇U − 𝑇𝑖 or integrate version is 𝑑𝑈 = 𝑛𝐶𝑣𝑑𝑇
𝑤 = -𝑃-./ ∆𝑉 = −𝑃𝑑𝑉
123
because q = 0, ∆𝑈 = 𝑤 and 𝑛𝐶𝑣𝑑𝑇 = − 𝑑𝑉
i
1no 123 3C 1no 3C 12
divide both sides by T -> 𝑑𝑇 = − 𝑑𝑉 -> 35 3
𝑑𝑇 = 35
− 𝑑𝑉
3 i3 i
3C iC
-> 𝑛𝐶𝑣𝑙𝑛 = −𝑛𝐶𝑣 ln
35 i5

V1 = 19.5L V2 = ? T1=335K, T2=?
123C
We know P2 = 0.225 bar so… 𝑉2 =
4C

pqrK
3C iC 3C sK
𝑛𝐶𝑣𝑙𝑛 = −𝑛𝐶𝑣 ln -> 𝑛𝐶𝑣𝑙𝑛 = −𝑛𝐶𝑣 ln pqrK
35 i5 35
sK
3C 3C 4
-> 𝑛𝐶𝑣𝑙𝑛 = −𝑛𝑅 ln + 𝑛𝑅𝑙𝑛( K )
35 35 4Y

2 <14Ct<145
𝑙𝑛𝑇2 = + 𝑙𝑛𝑇1 = 4.85 -> 𝑒 <13C = 𝑇2 = 128𝐾
nou2

oops.. I didn’t copy down ∆𝐻 or ∆𝑈