KFT232 Sem2 2011 2012
KFT232 Sem2 2011 2012
KFT232 Sem2 2011 2012
June 2012
Duration: 3 hours
[Masa : 3 jam]
Please check that this examination paper consists of THIRTEEN pages of printed
material before you begin the examination
Instructions:
Answer any FIVE (5) questions with at least ONE (1) question from Part B.
If a candidate answers more than five questions, only the answers to the first five
questions in the answer sheet will be graded.
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[KFT 232]
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PART A
1. (a) By giving examples, define the path (non-state) and state functions.
(3 marks)
(b) One mole of a gas at the temperature of 298 K and the pressure of 1 bar is
heated and compressed reversibly in a frictionless piston and cylinder to 573
K and 10 bar. Two paths were employed to achieve the final state as
illustrated in Figure 1. For this system,
(ii) Calculate the heat and work for both paths and comment weather they
are state or non-state functions.
Figure 1
(8 marks)
(c) Using the appropriate relations and thermodynamics laws, prove that:
(i) U H
V P
T T
(ii) 2 A CV
2
T V T
(9 marks)
2. (a) Describe the term ‘ideal solution’ based on the intermolecular forces of
liquids. Explain why a mixture of hexane and heptane forms ideal solutions.
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[KFT 232]
(3 marks)
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(b) An ideal mixture of benzene and methylbenzene is formed upon mixing. If the
vapour pressures of pure benzene and methylbenzene at 302 K are 32.6 kPa
and 30.1 kPa respectively, calculate the total pressure and the composition of
the vapour which is in equilibrium with a liquid mixture containing 100 g of
benzene and 80 g of methylbenzene at 302 K.
(10 marks)
(c) Derive the expressions for fugacity and fugacity coefficient for a gas which
obeys the following equation of state
𝑃𝑉𝑚 𝑎 𝑏
= 1 + + 2
𝑅𝑇 𝑉𝑚 𝑉𝑚
where a = -21.3 cm3 mol-1 and b = 1054 cm6 mol-2. Calculate the fugacity of
neon gas at 1 atm and 298 K.
(7 marks)
3. (a) Given that the entropy, S = f(T, P) and S = f(T, V), prove that:
∂V ∂P
CP - CV = T
∂T P
∂T V
(10 marks)
(b) At 27 oC and 1 bar, the volume of a NaCl solution in 1.0 kg methanol is given
by the following equation:
(i) Derive the expression for partial molar volume for NaCl
(ii) Calculate the partial molar volume for NaCl and methanol in 0.1 m
NaCl
(iii) Calculate the density of the 0.1 m NaCl solution
(10 marks)
4. A Carnot cycle uses 1 mol of a monatomic ideal gas as the working substance at an
initial state of 5 atm and 500 K. The gas expands isothermally to a pressure of 1 atm
(Step 1) and then adiabatically to a final temperature of 300 K (Step 2). This
expansion is followed by an isothermal compression (Step 3) and then by an
adiabatic compression (Step 4) back to its initial state. Determine the values of q, w,
H, U, S, G for each step and finally the Stot.
(20 marks)
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5. (a) For a chemical reaction described below and using the data given:
(b) Gas A forms an ideal solution with liquid B. At 350 K and the pressure
above the solution 760 Torr, a saturated solution formed and is found to have
a mole fraction of A, xA = 0.3017. At 200 K, gas A condensed to a liquid form
and is found to have an equilibrium vapour pressure of 11.47 Torr. Assume
that the vapour behaves ideally and that the heat capacity of the liquid and
the gas are the same at all temperatures. Compute the partial molar enthalpy
of vaporization and the normal boiling point of A.
(8 marks)
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[KFT 232]
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PART B
Answer at least ONE question.
6. (a) Write the overall cell reaction and calculate ∆G ° and the equilibrium
constant K at 25 °C for the reaction occurring in the following cells,
E°Zn2+Zn
= -0.7618 V
°
ECd2+ Cd = -0.403 V
(4 marks)
prove that
2𝑅𝑇 2𝑅𝑇
𝐸+ 𝑙𝑛 𝑚 = 𝐸 ° − 𝑙𝑛 𝛾±
𝐹 𝐹
(6 marks)
2𝑡−𝑅𝑇 𝑚1 𝛾±1
𝐸𝑐𝑒𝑙𝑙 = − 𝑙𝑛
𝐹 𝑚2 𝛾±2
(ii) Calculate the cell potential, given the mean activity coefficient, 𝛾± , of
the left and right side of the cell, 0.88 and 0.81, respectively, and the
transport number, t- =0.178.
(10 marks)
7. (a) The potential, Ф, on the ion due to the ionic atmosphere when the distance
from this selected ion, r, approaches the distance of closest approach, a, is
given by
Zi
4 1 a
2
and 2 =
kT i
N i Zi
2
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[KFT 232]
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where Ni and Zi represent the number per unit volume and the positive value
of the valence of the ith-type ion, respectively, is the electronic charge and ε
is the dielectric constant. Taking into account the deviations from ideality of
the behavior of a single ion of type i, the Gibbs energy could be expressed as:
Gi = Gio + kT In Cii
Z Z A I
-log
1 Ba I
where A and B are the Debye-Hückel constants and I is the ionic strength of
the solution.
(10 marks)
(b) The following rate constants were obtained for the reaction between
[CoBr(NH3)5]2+ ion (present in the form of Br-) and OH- ion (present as NaOH):
Make an estimate of the rate constant of the reaction at zero ionic strength
and the value of the product of the charge numbers.
(10 marks)
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[KFT 232]
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TERJEMAHAN
Sila pastikan kertas peperiksaan ini mengandungi TIGA BELAS muka surat bahan bercetak.
Arahan:
Jawab LIMA (5) soalan sahaja dengan sekurang-kurangnya SATU (1) soalan daripada
Bahagian B.
Anda dibenarkan menjawab soalan ini sama ada dalam Bahasa Malaysia atau Bahasa
Inggeris.
Jika calon menjawab lebih daripada lima soalan, hanya lima soalan pertama mengikut
susunan dalam skrip jawapan akan diberi markah.
Sekiranya terdapat sebarang percanggahan pada soalan peperiksaan, versi Bahasa Inggeris
hendaklah diguna pakai.
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[KFT 232]
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BAHAGIAN A
1. (a) Dengan memberikan contoh, takrifkan fungsi laluan (bukan fungsi keadaan)
dan fungsi keadaan.
(3 markah)
(b) Satu mol gas pada suhu 298 K dan tekanan 1 bar dipanaskan dan
dimampatkan secara berbalik di dalam omboh tanpa geseran dan silinder
kepada 573 K dan 10 bar. Dua laluan digunakan untuk mencapai keadaan
akhir seperti ditunjukkan dalam Gambarajah 1. Bagi sistem ini,
Gambarajah 1
(8 markah)
(i) U H U H
V P V P
T T T T
(ii) 2 A CV
2
T V T
(9 markah)
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[KFT 232]
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2. (a) Huraikan istilah ‘larutan unggul’ berdasarkan daya antara molekul bagi
cecair. Terangkan mengapa campuran heksana dan heptana membentuk
larutan unggul?
(3 markah)
(c) Terbitkan sebutan bagi fugasiti dan pekali fugasiti bagi gas yang mematuhi
persamaan keadaan berikut
𝑃𝑉𝑚 𝑎 𝑏
= 1 + + 2
𝑅𝑇 𝑉𝑚 𝑉𝑚
dengan a = -21.3 cm3 mol-1 dan b = 1054 cm6 mol-2. Kira nilai fugasiti bagi
gas neon pada 1 atm dan 298 K.
(7 markah)
∂V ∂P
CP - CV = T
∂T P
∂T V
(8 markah)
(b) Pada 27 oC dan 1 bar, isipadu larutan NaCl dalam 1.0 kg metanol diberikan
oleh persamaan berikut:
(10 markah)
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[KFT 232]
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4. Suatu kitaran Carnot menggunakan 1 mol gas monoatom yang bersifat unggul
sebagai bahan asas dengan keadaan awal 5 atm dan 500 K. Gas tersebut
mengembang secara isotermal pada tekanan 1 atm (Langkah 1) dan kemudiannya
mengembang secara adiabatik kepada suhu akhir 300 K (Langkah 2). Proses
pengembangan ini diikuti dengan proses pemampatan secara isotermal (Langkah 3)
dan balik kepada keadaan asalnya melalui proses pemampatan adiabatik
(Langkah 4). Tentukan nilai bagi q, w, H, U, S, G pada setiap langkah dan
akhirnya Stot.
(20 markah)
5. (a) Bagi tindak balas kimia yang ditunjukkan di bawah dan dengan menggunakan
data berikut:-
(b) Gas A membentuk larutan unggul dengan cecair B. Pada suhu 350 K dan
tekanan atas permukaan 760 Torr, suatu larutan tepu terbentuk dan didapati
pecahan mol A, xA = 0.3017. Pada suhu 200 K, gas A terkondensasi kepada
bentuk cecair dan didapati mempunyai tekanan wap keseimbangan 11.47
Torr. Anggapkan wap tersebut bersifat unggul dan muatan haba bagi cecair
tersebut adalah sama pada semua suhu. Kira entalpi molar separa
pengewapan dan takat didih normal bagi A.
(8 markah)
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[KFT 232]
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BAHAGIAN B
6. (a) Tulislah tindak balas sel keseluruhan dan kiralah ∆G o dan pemalar
keseimbangan, K pada 25°C bagi tindak balas yang berlaku dalam sel yang
berikut:
E°Zn2+Zn
= -0.7618 V
°
ECd2+ Cd = -0.403 V
(4 markah)
Buktikan bahawa
2𝑅𝑇 2𝑅𝑇
𝐸+ 𝑙𝑛 𝑚 = 𝐸 ° − 𝑙𝑛 𝛾±
𝐹 𝐹
(6 markah)
2𝑡−𝑅𝑇 𝑚1 𝛾±1
𝐸𝑠𝑒𝑙 = − 𝑙𝑛
𝐹 𝑚2 𝛾±2
(ii) Kiralah keupayaan sel. Diberi pekali keaktifan min, 𝛾± , bagi sel
setengah kiri dan kanan masing-masing ialah 0.88 dan 0.81, dan
nombor pindahan, 𝑡−=0.178.
(10 markah)
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[KFT 232]
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7. (a) Keupayaan, Ф, pada ion yang disebabkan oleh atmosfera ion, apabila suatu
jarak daripada ion terpilih ini, r, menghampiri jarak penghampiran yang
terdekat, a, diberi oleh
Zi
4 1 a
2
dan 2 =
kT i
N i Zi
2
dengan Ni dan Zi masing-masing mewakili bilangan per unit isipadu dan nilai
positif valensi ion berjenis i, ialah cas elektron dan ialah pemalar
dielektrik. Dengan mengambil kira penyelewengan daripada keunggulan bagi
kelakuan ion tunggal berjenis i, tenaga Gibbs boleh diungkapkan sebagai:
Gi = Gio + kT ln Ci i
Z Z A I
-log
1 Ba I
A dan B ialah pemalar Debye-Hückel dan I ialah kekuatan ion bagi larutan
ini.
(10 markah)
(b) Pemalar kadar yang berikut diperoleh bagi tindak balas antara ion
[CoBr(NH3)5]2+ (wujud dalam bentuk Br-) dan ion OH- (wujud sebagai NaOH)
Kiralah pemalar kadar bagi tindak balas ini pada kekuatan ion bernilai sifar
dan nilai hasil darab nombor cas.
(10 markah)
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[KFT 232]
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APPENDIX
Atomic Weights
-oooOooo-
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