Chem 3410, Solution for Assignment # 2, solution in red

(1) (i) If U is a state function then which of the following statement(s) is/are correct
about U:
f

(a) U = dU = Uf - Ui , The quantity dU is called an exact differential

i

(b) We cannot refer internal energy, U possessed by a system

(c) dU = Uf - Ui = 0 for a cyclic path
(d)

dU = Uf - Ui 0 for a cyclic path

(e) U is path dependent

(ii) Which of the following is/are not true about heat, q?
(a) Heat is transitory
(b) If the temperature of the surroundings is raised, q is positive
f

(c) q = dq = qf - qi
i

(d) The net effect of heat is to change the internal energy of the system and the
surroundings in accordance with the first law.
(e) q is a path function
(iii) Which of the following is/are not true about work, w?
(a) Work is transitory
(b) If the height of the mass of the surroundings is lowered work is negative
f

(c) w dw wf - wi
i

(d) dw is an exact differential

(e) w = U + q
(iv) Which of the following statement(s) is/are correct about enthalpy, H?
(a) H = U + PV
(b) H is state function
(c) H is an intensive property
(d) H has the units of height
(v) One mole of an ideal gas (Cp,m = 29.234JK-1mol-1) is expanded reversibly and
adiabatically from 1 dm3 to 10 dm3. If the initial temperature is 750 K, the final
temperature will be: (a) 1000 K, (b) 750 K, (c) 300 K, and (d) 100 K.

2. Show that (a) U = qv; (b) H = qp; and (c) Explain qualitatively why Cp > Cv for
gases?
Answer: see section 2.5 in your text book.
For Cp > Cv, please see page 27 in relation to figure 2.6.
3. From the variation of Cp, m of Cl2 with T as shown in the figure; explain the following:
(a) Cp, m rises rapidly with T, when T is between 20 to 175 K (Cl2 is solid).
(b) Cp, m increases and decreases discontinuously when solid Cl2 melts and liquid Cl2
vaporizes, respectively.
(c) Cp, m of gaseous Cl2 (T > 240K) increases sluggishly.
Ans: Please read page 26 - 27 in relation to figure 2.9.
4. What is wrong with the following statement? Because the well-insulated house stored
a lot of heat, the temperature didnt fall much when the furnace failed. Rewrite the
sentence to convey the same information correctly.
Ans: Still have problem? Please come on Friday afternoon 1:05 to 2:55 pm in Schrenk
G3.
5. (a) Draw a qualitative P-V diagram (which has same P and V value at 1-atm) for an
isothermal and adiabatic compression and expansion of an ideal gas.
(b)Explain why for compression starting at 1-atm Padia > Piso and for expansion
originating at 1-atm Padia < Piso.
Ans: Please read section 2.11 in relation to figure 2.17.
6. The temperature of 3.5 moles of an ideal gas increases from 15.3 C to 67.2 C as the
gas is compressed adiabatically. Calculate q, w, U, H for this process assuming that
Cv, m = 3R/2.

Alternatively, you can also use

H = nCp, mT

7. One mole of an ideal gas is subjected to the changes below. Calculate the change in
temperature (T) if CV, m = 3R/2.
q = -500 J, w = 150 J.
Ans: U = q + w = -500.00 J + 150.00 J = -350 J
Cv, m = 1.5 R = 1.5 x 8.314 J Mol-1 K-1 = 12.471 J Mol-1 K-1
As we know, U = n Cv, mT
U
350 Jmol 1
T =
=
= 28.065 K (since n = 1 mol)
Cv , m
12.471JK 1mol 1
Sample problems
1. Show for an adiabatic reversible compression or expansion of an ideal gas, PiVi = PfVf
( = Cp/Cv).
Ans: Please read section 2.11.
2. 3 moles of an ideal gas at 36.6 C expands isothermally from an initial volume of 25.0
dm3 to a final volume of 75.0 dm3. Calculate w for this process (a) for expansion
against a constant external pressure of 1.00x 105 Pa (Hints: make sure that you convert
to the right unit for work, see table 2.1) and (b) for a reversible expansion.
Pa x m3 = jule

= 5.00 x 103 J
= 8.487 x 103 J
3. In the reversible adiabatic expansion of 2.25 mol of an ideal gas from an initial
temperature of 32.0 C, the work done on the surroundings is 1450.00 J .If CV, m = 3R/2,
calculate q, w, U, and H.
Ans: Adiabatic process, q = 0
U = q + w = w = -1450.00 J (Note the negative sign: recall work done on the
surroundings is negative)
U = n Cv, m(Tf Ti)
-1450.00 J = 2.25 mol x 3/2 x 8.314 J mol-1K-1 (Tf 305.15 K)
Tf = 253.46 K
H = n Cp, m (Tf Ti) = n (Cv, m + R) (Tf Ti)

CP Cv = nR, Cp,m Cv,m = R

= 2.25 mol(3/2 R + R) (253.46 K 305.15 K)

= 2.25 mol x 5/2 x 8.314 J mol-1 K-1 x 51.69 K
= 2417.35 J
Alternatively, you can also use, H = U + nR T

4. (i) From the plot (given on the right) of molar heat

capacities, CV, m against temperature explain the following
from the microscopic point of view:
(a) Helium has a very low value of CV, m and is invariant
with temperature.
(b) At low temperature ~300 K, CV, m is greater for CO than
He.
(c) At higher temperatures, T > 300 K, CV, m is much
greater for C2H4 than CO2 or CO.
Ans: Please read section 2.5 in relation to figure 2.8

Important:
Sections and page numbers mentioned above are from the 3rd edition of the text book.
2nd edition readers may check with me to get the right section and page numbers but
often it is very obvious.