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Physical Cehmistry Questions
CHEMISTRY
MET (201)
GENERAL QUESTIONS ON THE
COURSE CONTENTS
PREPRED BY: DR. FAWZI A. A. ELREFAIE
For
The Second Year Metallurgy
Faculty of Engineering
Cairo University
(2014/2015)
1
PHYSICAL
CHEMISTRY
MET (201)
Questions on
INTRODUCTION AND
DEFINATION OF TERMS
2
Group (1)
3
6. Complete:
R= 0.082 ………/………
R = 8.3144 ……. /………
R = 1.987 ……..../……....
4
Group (2)& Group (3)
13. Complete:
The mechanical equivalent of heat = ………… .
6
18. Derive the following relation:
𝒅𝑽 𝒅𝑼
𝑪𝒑 − 𝑪𝒓 = ( )𝑷 (𝑷 + ( )𝑻 )
𝒅𝑻 𝒅𝑽
Based on this equation, prove that:
𝑪𝒑 − 𝑪𝒗 = 𝑹
𝒅𝑽
19. Based on Joule’s experiment, show that ( )𝑷 = 𝟎for
𝒅𝑻
ideal gases.
7
23. Two closed systems that each has the same P-V state,
draw schematically the P-V figures for each on the
same diagram.
8
Group (4)
9
Group (5) & Group (6)
10
When a system undergoes a reversible process, no
entropy is ……, i.e. ∆𝑺𝒊𝒓𝒓 =……., entropy is simply
……… from one part of the system to …… part.
34. Define the heat engine. Explain the following
statement: “it is impossible to create perpetual motion
machine of the second type”.
11
Group (7)
12
Group (8)
14
Group (9)
50. Explain why if the A-B bond in much different than the
A-A bond or B-B bond in the binary mixing of A and
B, ideal mixing does not occur.
16
Group (10)
51. Show how the combination of the 1st and 2nd laws of
thermodynamics leads to the following function:
𝑼 = 𝒇(𝑺, 𝑽)
if the work performed by the system is (WP-V) only.
52. What are the criteria for equilibrium that are provided
due to the combination of the 1st and 2nd laws of
thermodynamics?
17
55. Define the Helmholtz free energy function (work
function), A. Show that:
𝑨 = 𝒇(𝑽, 𝑻)
−𝑾 ≤ −∆𝑨
(𝑾𝒎𝒂𝒙 ) = −∆𝑨
For spontaneous processes that occur at constant T and
V; dA ˂ 0, equilibrium occur at the minimum value of
A, i.e. at dA = 0.
18
Group (11)
57. Define the Gibbs free energy in terms of H and TS; and
in terms of U, PV, and TS. Then prove that:
𝐺 = 𝑓 (𝑃, 𝑇),
(𝑊 ′ ) ≤ −∆𝐺,
(𝑊 ′ ) = −∆𝐺, and
𝑑𝐺 = 0
What are the conditions required for the validity of each
of the previous equality and inequality.
19
61. Drive the equation of state that relates the internal
energy of a closed one-component system to the
experimentally measurable quantities T, and P. By
using this relation prove that: dU = CvdT for ideal gas.
Also prove U is independent of its pressure.
20
Group (12)
21
Group (13)
𝑷𝟐
∆𝑺 = − ∫ 𝜶𝑽𝒅𝑷
𝑷𝟏
𝑻𝟐 𝑷𝟐
∆𝑺 = ∫ 𝑪𝒑 𝒅𝒍𝒏𝑻 − ∫ 𝜶𝑽𝒅𝑷
𝑻𝟏 𝑷𝟏
22
73. State the Nernst postulate for the third law of
thermodynamics; Plank’s pointed out that this
statement, why? To overcome this incompetence,
Plank’s formulated another postulate, write this
postulate.
23
Group (14)
𝑷𝑽
78. Define the real gases in terms of 𝒁 = . Let
𝑹𝑻
𝒁 = 𝒎𝒃 + 𝟏, as for hydrogen gas, relate P to V at
constant T.
80. Write down Van Der Waal’s equation for a real gas at
constant T which is less than Tcr; what is the meaning
of the constants a andb of Van Der Waal’s equation.
What is the type of Van Der Waal’s equation?
Calculate the values of Pcr, Vcr, and Tcr in terms of a, b,
and R.
24
The isothermal compressibility factor of the gaseous
phase as compared to the same parameter of the
liquid phase in equilibrium with the gaseous phase at
the same temperature,
The variation of molar volume of the gas with
temperature, and
The variation of molar volume of the liquid phase
with temperature.
25
Group (15)
∆𝑯(𝒊) = 𝟎
∆𝑯𝒎 = 𝟎
∆𝑮𝒎 = 𝑹𝑻 ∑ 𝒙(𝒊)𝒍𝒏𝒙(𝒊)
∆𝑺𝒎 = −𝑹 ∑ 𝒙(𝒊)𝒍𝒏𝒙(𝒊)
26
86. Define the fugacity term. Prove that𝒇 = 𝑷𝟐 /𝑷𝒊𝒅𝒆𝒂𝒍 , for
a gaseous system whose equation of state is given by:
𝒇 𝒛−𝟏
𝑷(𝒗 − 𝒃) = 𝑹𝑻. Also prove that 𝒅𝒍𝒏 ( ) = ( ) 𝒅𝑷.
𝑷 𝑷
87. For Van der Waal’s isothermal shows in the following
figure, show how to apply the integration:
𝑷𝒊
𝑮(𝒊) = 𝑮(𝑨) + ∫ 𝑽𝒅𝑷
𝑷𝑨
At the points B, C, D, E, F, G, H, I, J, K, L, M, N, and
O.
Show that G-P curve you obtain on G-P diagram.
Explain the G-P results you obtain.
27
Group (16)
28
°
𝑷(𝑪)
∆𝑮 = −𝑹𝑻𝒍𝒏 = −𝑹𝑻𝒍𝒏𝑲𝒑
𝑷(𝑨)𝑷(𝑩)
29
Group (17)
Group (18)
94. By considering the reaction:
𝟏
𝑴(𝒔) + 𝑶𝟐 (𝒈) = 𝑴𝑶(𝒔)And through
𝟐
the equilibrium that occurs between the equilibrium that
occurs between the vapors of the pure solid phases each
at (P,T) and oxygen, also at (P,T), prove that the
equilibrium of the above mentioned reaction occurs if:
𝟏
°(
∆𝑮 𝑹) = −𝑹𝑻𝒍𝒏(𝟏/𝑷(𝑶𝟐 ) ) 𝟐
31
96. Write the three different relations that may be obtained
by fitting the experimentally measured values of
∆𝑮° (𝑹) at different values of T.
Group (19)
97. Complete:
Experimentally Ellingham found that the (∆𝑮° − 𝑻)
relation for the oxidation of a series of pure metals by
oxygen to form pure metal oxides is given by the
relation: ∆𝑮° = ⋯ + ⋯
The intercepts of an Ellingham line with ∆𝑮° axis at
T = 0K represents …… of the oxidation reaction
𝑴 + 𝑶𝟐 = 𝑴𝑶𝟐 and∆𝑺° (𝑹)is the ……..
∆𝑆 ° (𝑅) is given by: ∆𝑺° (𝑹) = ⋯
∆𝐺 ° (𝑅) is given by: ∆𝑮° (𝑹) = 𝑹𝑻 … …
At the horizontal line ∆𝐺 ° = 0, 𝑷(𝑶𝟐 ) = ⋯ atm.
The temperature at which Ellingham line intercepts
with the horizontal line ∆𝐺 ° = 0 represents the …,
…, … equilibrium under 𝑷(𝑶𝟐 ) = ⋯; under this
temperature, … will be spontaneous; if the
temperature is higher, the … reaction of MO will
spontaneously occur.
32
If ∆𝐶𝑝 = 0, ∆𝐻 ° value will be linearly … of
temperature, and 𝑇∆𝑆 ° will be … dependent.
If ∆𝑆 ° for two oxidation reaction are identical, the
relative stabilities of the two oxides depend on the
∆𝐻 ° values of the two reactions.
The more … the value of …, the more stable the
oxide.
If the two ∆𝐺 ° − 𝑇 lines representing the oxidation of
two metals intersects at temperature TE, the
intersection point represents the equilibrium:
𝐵 + ⋯ = 2𝐴 + ⋯
Below TE …, … are stable while, above TE …, … are
the stable phases.
At T ˂ TE, … reduces … to form … + BO2.
33
100. Superimpose the Ellingham line for the oxidation
reaction: 𝟐𝑨 + 𝑶𝟐 = 𝟐𝑨𝑶 whose ∆𝑮° at
200k = -200,000 joule, and at 1200k = 100,000 joule on
the Richardson lines whose P(O2) = 10, 1, 10-4, 10-8,
and 10-20 atm. From this diagram determine the
temperatures at which the system A, AO2, O2
equilibrate at the mentioned oxygen pressures.
Group (20)
101. Discuss in-detail the effect of the phase transformation
of solid metal to liquid metal, and from solid metal
oxide to liquid metal oxide on the Ellingham line that
represents the oxidation of this metal. Show this effect
diagrammatically on the (∆𝐺 ° − 𝑇) Ellingham line for
the following two cases:
𝑇𝑚 (𝑀) < 𝑇𝑚 (𝑀𝑂)
𝑇𝑚 (𝑀) > 𝑇𝑚 (𝑀𝑂)
35
Calculate the equilibrium temperatures of the system M,
MO, CO, CO2 at the mentioned pressures if ∆𝐺 ° values
for the reaction 𝑀 + 𝑂2 = 𝑀𝑂2 are -600,000
joules/mole O2 at 200K and -300,000 joules/mole O2 at
800K. Also, construct the CO/CO2 scale for this system.
36
108. Prove that for a second-order reaction:
If 𝐶𝑜 (𝐴) > 𝐶𝑜 (𝐵):
𝑪𝒐 (𝑩)(𝑪𝒐 (𝑨) − 𝒙) 𝑲
[𝑪𝒐 (𝑨) − 𝑪𝒐 (𝑩)]𝒍𝒐𝒈 = 𝒕,
( )
𝑪𝒐 (𝑨)(𝑪𝒐 𝑩 − 𝒙) 𝟐. 𝟑𝟎𝟑
If 𝐶 (𝐴) = 𝐶 (𝐵) = 𝐶:
𝒙
= 𝑲𝑻
𝑪𝒐 (𝑪𝒐 − 𝒙)
𝟏
𝒕𝒐.𝟓 =
𝑲𝑪𝒐
109. Complete:
The effect of temperature on reaction rate constant is
given by ……… equation, which is mathematically
expressed by:
k = ………
Logk = ……… - 0.4342 ………/………
Define the constants of this equation.
1
The slope of the straight line 𝑙𝑜𝑔𝑘 − equal to
𝑇
………
The half-life period of a reaction of an overall order n
is given by:
𝑡0.5 = ………
or, log(𝑡0.5 ) = ………
The slope of the straight line log(𝑡0.5 ) = 𝑙𝑜𝑔𝐶𝑜 =….
37
PHYSICAL
CHEMISTRY
MET (201)
GENERAL QUESTIONS (2)
38
110. Write short notes on:
Simple equilibrium.
Extensive and intensive properties, give examples.
Homogenous and heterogeneous systems.
The historic development of the relationship between
heat and work. Ending by the mechanical equivalent
of heat.
The first law of thermodynamics and the
impossibility of constructing a perpetual motion
machine of the first kind.
39
112. For real gases that obey the equation of state:
𝒂
(𝑷 + ( 𝟐 )) (𝒗 − 𝒃) = 𝑹𝑻
𝒗
Prove that: 𝒖 = 𝒇(𝒗, 𝑻).
𝑇
128. Prove that: 𝑆𝑇 = 𝑆𝑜 + ∫𝑇 2 𝐶𝑝 𝑑𝑙𝑛𝑇(state the
1
conditions).
43
What is the incompetence of each of the previous
postulates?
134. What is the condition that must exist to apply the relation:
1 1
𝑡0.5 = ( )( 𝑛−1 )
𝐾 𝐶𝑜
How to evaluate the value of n?
45