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TABLE OF TOPIC SPECIFICATION FOR SET-1 EXAM

TOPIC Items
Matter and energy
Theory of atoms and molecules
Balancing Chemical Reaction 2
Chemical Periodicity 3
Calculation Principles in Chemical Changes (Stoichiometry)
General Chemistry Chemical Bonding
Solutions 5
Chemical Equilibrium 1
Chemical Kinetics 5
Nuclear Chemistry 9
Group II and Group VII
Introduction to the chemistry of transition element
Solid state: Crystalline and Amorphous solids
TOPIC
Chemical Bonding and Properties of Organic Compounds 2
Hydrocarbons (alkanes, alkenes, alkynes) 2
Aromatics 2
Organic Chemistry
Halogen compounds 1
Hydroxy compounds (including ethers and epoxides) 2
Carbonyl Compounds: Aldehydes 2
Carbonyl Compounds: Ketones 2
Carboxylic acids and Derivatives 1
TOPIC
Carbohydrates 1
Amino acid, Proteins, Enzymes: Structure and Function 5
Lipids and Fats
Biochemistry
Nucleic acids
Enzyme kinetics
Techniques in Biochemistry and Industrial uses of enzymes
Introductory topics in metabolism (including photosynthesis) 1
TOPIC
Concepts and Calculations
(Ionic Equilibria, salt hydrolysis, Le Chatelier) 9
Units of concentrations, pH and buffer problems 4
Applications of Gravimetry and UV-Vis Spectroscopy 2
Analytical Chemistry
Applications of Acid Base titration 2
Applications Precipitation titration 3
Applications of Redox titration 2
Applications of Complex Formation titrations 2
TOPIC
Properties of Gases (real gas, molecular collisions, effusion) 4
Properties of Solutions (colligative properties) 2
First Law of thermodynamics 6
Second Law of thermodynamics 1
Physical Chemistry Thermochemistry 1
Thermodynamics of Vapour Pressure 3
Chemical Equilibrium: Homogeneous and Heterogeneous
Phase Equilibria
Electrochemistry
Conductance and Mobility in ionised solutions
Chemical Kinetics
Miscellaneous Topics TOPIC

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Anything chemistry or chem eng'g related/ recent events of interest to
the chemistry and chem eng profession 11
TOPIC
Environmental Sci. Conceptual
BOD, COD 2

CHEMICAL ENGINEERING PRE-BOARD REFRESHER EXAMINATION


DAY 1: Physical and Chemical Principles

ANSWER KEY
1. Which of the following can function as a chelating agent?
a. SH- c. H2NCH2CO2 -
b. H2O d. SCN-
Answer: C (bidentate, tridentate, etc, ligand will give a chelate)
2. Transuranic elements have atomic numbers greater than Uranium -92 and many are named after people like
Einstein, Fermi or Nobel. Only one non-transuranic element is named after a person, what is this element?
a. Gadolinium c. Terbium
b. Samarium d. Neodymium
Answer: Gadolinium, atomic number 64, a silvery metal discovered in 1880 by J.C. Galissard de Marignac, and named
after J. Gadolin, a Finnish chemist. Gadolinium is used in high-strength magnets for recording heads.
3. The radioactive isotope 210 84Po was said to be the agent that poisoned the former Russian security agent
Alexander Litvenenko in London in November 2006. 210 84Po decays to give an element X and emits a high energy
alpha particle (which is a helium nucleus, 4 2He). No other particle is produced. Alpha particles cause irreparable
damage to the tissues of internal organs.
210 4
84Po  2He + X

Which row in the table correctly describes the nuclear make-up of 210 84Po and element X

210
84Po X
Number of Number of Number of
neutrons protons neutrons
A 126 80 122
B 126 82 124
C 210 80 206
D 210 82 208
Solution:
No of protons of Po = 84
No if nucleons of Po = 210
Therefore, number of neutrons = 210 – 84 = 126

When alpha particle is emitted :


No of protons of X = 84-2 = 82
No of neutrons of X = 126 – 2 = 124
Thus, 210 84Po  4 2He + 206 82X

4. Balance the following chemical reaction: ___C5H8O2 + ___NaH+___ HCl → ___ C5H12O2 +___ NaCl
a. 1,1,2,1,2 b. 1,2,2,1,2
c. 2,2,1,2,1 d. 2,1,2,1,2

Answer: b
5. Calculate the Kc for the reaction: N2(g) + 3 H2(g) ↔ 2 NH3 (g) at 50 oC if Kp is 1.50 x 10-5 /atm2
a. 3.00 x 10-2 L2/mol2 b. 5.80 x 10-2 L2/mol2
-2 2 2
c. 5.09 x 10 L /mol d. 6.04 x 10-2 L2/mol2

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Solution:
Delta n = 2-4 = -2 …. T = 500 oC + 273 = 773 K
Kp = Kc(RT)delta n
1.50 x 10-5 /atm2 = Kc {0.0821 L.atm/K.mol (773)}-2
1.50 x 10-5 /atm2 = Kc / (63.5 L atm/mol)2
Kc = 1.50 x10-5/atm2 (4.03 x 103 L2 atm2 /mol2) = 6.04 x 10-2 L2/mol2

6. Which alcohol will undergo acid-catalyzed dehydration under the mildest conditions?
(A) CH3CH2CH2CH2OH (B) CH3CH2CH(OH)CH3 (C) (CH3)2CHCH2OH (D) (CH3)3COH

Solution: D will give a tertiary carbocation which is the stable type.


7. The ______ sphere is enclosed in brackets in formulas for complex species, and it includes the central metal ion
plus the coordinated groups.
a. ligand b. donor
c. coordination d. chelate

Solution: Coordination sphere = Metal ion + ligand


8. In DAO 34, this is a class of fresh surface water used for primary contact recreation such as swimming, bathing,
diving, etc.
a. Class AA b. Class B
c. Class C d. Class D

Solution:
Class AA -
Class B-
Class C-
Class D-

9. In 2018, ______________ received the prestigious 2018 Nobel Prize in Chemistry for the pioneering work that
mimics evolution to engineer enzymes.
a. Koichi Tanaka b. Hideki Shirakawa
c. Frances Arnold d. Richard Henderson

Solution:
Koichi Tanaka - Japanese engineer who shared the Nobel Prize in Chemistry in 2002 for developing a novel method
for mass spectrometric analyses of biological macromolecules.

Hideki Shirakawa- Japanese engineer and chemist. He is best known for his discovery of conductive polymers.

Frances Arnold - born July 25, 1956, is an American chemical engineer and Nobel Laureate. She is the Linus Pauling
Professor of Chemical Engineering, Bioengineering and Biochemistry at the California Institute of Technology
(Caltech).

Richardson Hendderson- a Scottish molecular biologist and biophysicist and pioneer in the field of electron
microscopy of biological molecules.

10. A vitamer of a vitamin is any of several chemical compounds that have a similar molecular structure of that
vitamin class. Which is a vitamer of vitamin K.
a. Phylloquinone b. Tocopherols
c. Riboflavin d. Retinal

Solution:
Phylloquinone – Vitamin K1 (other include Menaquinone-K2)
Tocopherols – Vitamin E
Riboflavin – Vitamin B2 (biotin- vitamin B12 )
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Retinal- Vitamin A
11. To determine the mass of K3PO4 from the given mass of K2PtCl6, the gravimetric factor to be used is
a. FM of K3PO4 / FM of K2PtCl6 b. 3 FM of K2PtCl6 / 2 FM of K3PO4
c. 2 FM of K3PO4 / 3 FM of K2PtCl6 d. FM of K3PO4 / 3 FM of K2PtCl6

Solution: G.F = (FM substance sought / FM substance weighed) (x/y)


12. Which solution has the greatest percent ionization?
a. 0.10 M acetic acid (Ka = 1.8 x 10–5) b. 0.10 M formic acid (Ka = 1.8 x 10–4)
–5
c. 0.010 M acetic acid (Ka = 1.8 x 10 ) d. 0.010 M formic acid (Ka = 1.8 x 10–4)

Solution: Higher Ka, stronger acid, more tendency to ionise or give protons
More dilute, higher ionisation

13. An aqueous solution contains 30.0 g of protein in 1.00L. The osmotic pressure of the solution is 0.0167 atm at
25oC. What is the approximate molecular of the protein?
a. 4.39 x 104 g/mol b. 2.20 x 104 g/mol
4
c. 6.83 x10 g/mol d. 3.50 x 104 g/mol

Solution: π = (n/V)RT
0.0167 atm = ( n / 1.00L) (0.0821 L.atm/(K.mol)) (298K)
n = 6.83 x10 -4 mol
Therefore, MW protein = 1 mol protein (30.00 g protein/ 6.83 x 10-4 mol) = 4.39 x 104 g /mol

14. 52 Mn undergoes radioactive decay to give 52 Cr by what decay mode?


a. Alpha emission b. Beta emission
c. Positron emission d. Gamma emission
Solution: Positron emission (β+ decay) is the emission of a positron from the nucleus. Manganese-25 is an example of
a nuclide that undergoes positron emission: 5225 Mn  0+1 e + 5224 Cr

Positron emission is observed for nuclides in which the n:p ratio is low. These nuclides lie below the band of stability.
Positron decay is the conversion of a proton into a neutron with the emission of a positron. The n:p ratio increases,
and the daughter nuclide lies closer to the band of stability than did the parent nuclide.

15. Heptane and Octane from ideal solutions. What is the vapour pressure at 40oC of a solution that contains 3.00
mol of heptane and 5.00 mol of octane? The vapour pressure of heptane is 0.121 atm and the vapor pressure of
octane is 0.041 atm.
a. 0.053 atm b. 0.800 atm
c. 0.071 atm d. 0.710 atm

Solution: mol fraction (X) octane = (5.00/8.00) = 0.625


mol fraction (X) heptane = (3.00/8.00) = 0.625
Total Vapour Pressure = XoctanePoctane + XhepatanePheptane = 0.375 (0.121atm) + 0.625(0.041 atm)= 0.071 atm

16. Sulphur dioxide is soluble in water, KH = 1.8 x 10-5 mol L-1 Pa-1 at 25o C. Calculate the pH of rainwater that is in
equilibrium with air that has an SO2 (g) concentration of 2 ppm. Given that Ka1 = 1.72 x 10-2.
a. 7.00 b. 4.01
c. 5.10 d. 3.60

Solution: The sulphur dioxide reacts with water to form sulphurous acid (SO2 + H2O ⇄ H2SO3).
Assuming a total pressure of one atmosphere, the PSO2 = (1 atm) (2x10-6) =2.0 x 10-6 atm.
Converting the given KH into atmospheres yields; 1.8 x 10-5 M Pa-1 x 101,300 Pa atm-1 = 1.82 M atm-1
Thus, [SO2(aq) ] = KH x PSO2 = (1.82 M atm-1 ) (2.0 x 10-6 atm) = 3.64 x 10-6 M

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Note: We cannot use an ICE (initial change equilibrium) table because SO2 will not be depleted from the gas phase
and H2SO3 will be constant, we can expect that [H+] = [HSO3 - ] (assuming no other sources of H+ ). Using the Ka1
expression and assuming no further dissociation of HSO3 –
Ka1 = x2/[SO2 (aq)]
where x = [H+ ] = [HSO3- ] and we assume that the atmosphere provides an inexhaustible supply of SO2(aq)
[H+ ]2 = (1.72 x 10-2 ) (3.64 x 10-6 ) = 2.50 x 10-4 M
pH = 3.60

17. Which of the following titrants would give the sharpest change in voltage (i.e., the steepest titration curve) for
a given analyte?
a. I3- b. MnO4-
c. Cr2O72- d. H2O2
Solution:
Strengths of REDOX Titrants: MnO4- > Ce4+ > Cr2O4-2 > I3- (H2O2 is NEVER used as a titrant!)
Stronger the titrant, the steeper the equivalence point region!

18. A solution of a salt of which metal produces a bright red colour in a flame test?
a. lithium b. sodium
c. potassium d. copper
Solution
Lithium – red Barium – pale green
Sodium – yellow Strontium - red
Potassium – pink Calcium – orange-red
Copper – blue-green

19. A 345. 0 – mg sample of a pure unknown monoprotic acid is dissolved and titrated with 27.40 mL of 0.100 M
NaOH. What is the formula weight of the acid?
a. 125.9 g/mol b. 130.1 g/mol
c. 210.0 g/mol d. 60.01 g/mol

Solution: (27.40 mL)(0.100 mmol/mL) (F.Wt.) = 345.0


F.Wt. =125.9 g/mol

20. Kevlar is a heat-resistant and strong synthetic fibre, related to other aramids such as Nomex and Technora.
Kevlar has many applications, ranging from bicycle tires and racing sails to bulletproof vests. Kevlar
is synthesized in solution from the monomers consisting of two monomers. What are these monomers?
a. 1,4-phenylenediamine and terephthaloyl chloride b. adipic acid and 1,6 Hexamethylenediamine
c. phenol and formaldehyde d. ethylene glycol and terephthalic acid.

Solution: 1,4-phenylene-diamine and terephthaloyl chloride are monomers for Kevlar: Condensation reaction

b. adipic acid and 1,6 Hexamethylenediamine -> Nylon 6,6


c. phenol and formaldehyde – Bakelite
d. ethylene glycol and terephthalic acid.- Dacron (he continuous filament yarn is used in curtains, dress fabrics, high-
pressure fire hoses, men's shirts, and thread)

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21. A sample of a wooden artefact at the Philippine National Museum is found to undergo 9.0 146C disintegrations
per minute per gram of carbon. What is the approximate age of the artefact? The half-life of 146 C is 5730 years,
and the radioactive activity of wood recently cut down is 15 disintegrations per minute per gram carbon.

a. 5.0 x 103 years b. 3.0 x 103 years


c. 2.2 x 103 years d. 4.2 x 103 years

Solution:
Use the half-life for radioactive decay of 146C to find the rate constant, k,
k = 0.693/ t1/2 = 0.693/ 5730 = 1.21 x 10-4 / year
The ratio of the radio carbon activity per gram carbon for the wood recently cut down was 15 disintegrations /
minute to the radioactive carbon for the object (9.0 disintegrations per minute) Is equal to No/N
Log (No/N) = kt/ 2.30
Log (15 disintegrations per minute / 9.0 disintegrations per minute) = (1.21 x 10-4/year) t / 2.30
T = 2.30 (log 1.67) / 1.21 x10-4/year = 4.2 x 103 years

22. Consider the reaction: 2 NOCl(g) à 2 NO(g) + Cl2 (g), the rate equation is: Rate of production of Cl2 = k [NOCl]2
The rate constant, k, is 2.6 x 10-8 L/(mol·s) at 300. K and 4.9 x10-4 L/(mol·s) at 400. K.
What is the activation energy, Ea, for the reaction?
a. 100 kJ/mol b. 90 kJ/mol
c. 98.0 kJ/mol d. 75 kJ/mol
Solution: Arrhenius Equation:
Ea = 2.303 R [(T1T2)/(T2-T1) ] log (k2/k1)
Ea = 2.303 (8.314 J/mol.K) [(300.K x 400.K)/ (400-300)] log ( 4.9 x 10-4/2.6 x10-8)
Ea = 19.1 J/mol.k (1200 K ) log (1.88 x104) = 22,900 J.mol (4.28) = 98,000. J/mol = 98.0 kJ/mol

23. What is the product of alpha emission from the isotope Uranium-238?
a. 232 Th b. 234 Th
c. 237 Np d. 231 Pa

Solution: Alpha (α) decay is the emission of an α particle from the nucleus. For example, Uranium-238 undergoes α
decay: 238 92 Uranium  4 2 He + 234 90 Th (He is an alpha particle)

Alpha decay occurs primarily in heavy nuclei (A > 200, Z > 83). Because the loss of an α particle gives a daughter
nuclide with a mass number four units smaller and an atomic number two units smaller than those of the parent
nuclide, the daughter nuclide has a larger n:p ratio than the parent nuclide. If the parent nuclide undergoing α decay
lies below the band of stability the daughter nuclide will lie closer to the band.

24. Calculate the osmotic pressure of blood at normal body temperature (37oC) if the blood behaves as if it were
0.296 M solution of a non-ionizing solute.
a. 762.9 atm b. 7.53 atm
c. 7.0 atm d. 700 atm

Solution: π = MRT = (0.296 mo/L) ( 0.0821 L.atm/(K.mol) ) (310 K) = 7.53 atm


π = osmotic pressure

25. CH3NH2, methyl amine is a weak base with a Kb of 4.38 x 10¯4. What would be the pH of a solution of 0.350 M
methyl ammonium chloride, CH3NH3+Cl¯?
a. 5.5 b. 7.5
c. 5.0 d. 4.5

Solution: CH3NH3+ + H2O ⇌ CH3NH2 + H3O+


Kw = K a Kb
1.00 x 10¯14 = (x) (4.38 x 10¯4)
x = 1.00 x 10¯14 / 4.38 x 10¯4 = 2.2831 x 10¯11
We now calculate the [H3O+] using the Ka expression:
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2.2831 x 10¯11 = [(x) (x)] / (0.350 − x)
neglect the minus x
x = 2.8268 x 10¯6 M
Since we have the [H3O+], our last step will be to calculate the pH:
pH = −log 2.8268 x 10¯6 = 5.549

26. A solution is prepared by dissolving 0.300 g of an unknown non-volatile solute in 30.0-g carbon tetrachloride
has a boiling point that is 0.392oC higher than that of pure CCl4. Given the ebullioscopic constant to be + 5.02
o
C/m. What is the molecular weight of solute?
a. 130 b. 384
c. 100 d. 128

Solution: tb = m kb  +0.392oC = m + 5.02 oC/m  m = 0.0781 m


Find the number grams solute dissolved in 1000 g CCl4 (NOTE: molality = mol/kg solvent)

? g solute = 1000 g (0.300 g solute / 30.0 g CCl4) = 10.0 g of CCl4


Since the solution is 0.0781 m, 10.0 g of solute is 0.0781 mol solute

? g solute = 1 mol solute (10.0g solute / 0.0781 mol solute) = 128


The molecular weight of solute is 128

27. What is the Vant Hoff factor for the reaction: Fe2(SO4)3(s) →2 Fe3+(aq) + 3 SO2-4(aq)
a. 4 b. 3
c. 3 d. 5

Solution: The van't Hoff factor, i, is the number of particles formed in a solution from one formula unit of solute. i is
a property of the solute. In an ideal solution, i does not depend on the concentration of the solution.

28. The reaction takes place in a basic solution: ___H2O + ___MnO4- + ___C2O42- → ___MnO2 + ___OH- + ___CO2.
What are to coefficients of the balanced reaction?
a. 4, 3, 2 ,2, 8 ,6 b. 2, 4, 3 ,2 , 8 ,6
c. 4, 2, 3,2, 8 ,6 d. 3, 2, 4 ,2 , 8 ,6

29. What is the role of hydroxide ion in the reaction below?


CH3CH2CH2CH2Br + OH–  CH3CH2CH2CH2OH + Br–
a. Oxidizing agent b. Nucleophile
c. Lewis acid d. Catalyst

30. The sequence of amino acids in a protein is known as its…


a. primary structure b. secondary structure
c. tertiary structure. d. quaternary structure.

31. Molecules from which class of biopolymers can react with water, in the presence of suitable enzymes, to form
smaller examples of that class of biopolymers?
I. Proteins II. Polysaccharides III. Lipids
a. I only b. Both II and III only
c. Both I and II d. Both I nor III

32. A newly synthesized organic reagent is found to form a complex with calcium (II). To learn more about the
nature of the complex, a 50.0- mg sample of the ligand (FM = 181.2) is titrated with calcium (II) using a calcium-ion
electrode to detect the titration end point. The titration requires 11.46 mL od 0.0120 M calcium chloride. What is
the formula for the complex?
a. Ca(Ligand)1 b. Ca(ligand)3
c. Ca(Ligand)2 d. Ca(ligand)4

Solution:
(11.36 mL )( 0.0120 M) = 0.136 mmol Ca

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50.0-mg/ 181.12 = 0.276 mmol reagent
Combining ratio Ca:reagent = 0.136 mmo/ 0.276 mmol = 0.498,
Combining ratio Reagent: Ca = 0.276 mmol/ 0.136 mmol = 2.0 therefore, complex is Ca Reagent2

33. Which of the following method-indicator pairs is NOT CORRECT?


a. Fajans – dichlorofluorescien b. Leibig – Ag[Ag(CN)2]
c. Iodometry – starch d. Mohr – Cr2O72-
Solution: Potassium Chromate K2CrO4 is the indicator for mohr method

34. Calculate the pH of the solution that results from the addition of 0.040 moles of HNO3 to a buffer made by
combining 0.500 L of 0.380 M HC3H5O2 (Ka = 1.30 x 10¯5) and 0.500 L of 0.380 M NaC3H5O2. Assume addition of the
nitric acid has no effect on volume.
a. 4.70 b. 4.00
c. 4.50 d. 4.20

Solution:
1a) The nitric acid will reduce the amount of NaC3H5O2:
(0.380 mol/L) (0.500 L) = 0.190 mol of NaC3H5O2
0.190 mol − 0.040 mol = 0.150 mol NaC3H5O2 remaining

1b) The reaction in 1a will increase the amount of HC3H5O2:


the increase will be by the same amount of the decrease
0.190 mol + 0.040 mol = 0.230 mol of HC3H5O2

2) Calculate the new pH: Use Henderson- Hasselbalch


pH = pKa + log ([base] / [acid])
pH = 4.886 + log (0.150 / 0.230)
pH = 4.700

35. The radioactive nuclide 60 27Co has a half-life of 5.27 years. Calculate the mass of 60
27Co that remains from a
0.100 g sample of the nuclide after 1.00 year has elapsed.
a. 0.1040 g b. 0.00877 g
c. 0.0123 g d. 0.1004 g

Solution:
k = 0.693/ t1/2
k = 0.693/ 5.27 year = 0.132/year

The mass of 60 27Co remaining at the end of 1.00 year may be fund using
Log (No/N) = kt / 2.30
Log (No/N) = [(0.132/year) (1.00 year)/ 2.30] = 0.0574
No/N = antilog 0.0574 = 1.14
Therefore, 0.0100 g/ N = 1.14  N = 0.00877 g

36. Find number of protons and mass number of Y in to balance the reaction: 92234X + β- + α → Y + γ + 2β+
a. 91240Y b. 89 239Y
c. 90238Y d. 91
238
Y

Solution: Number of protons in left side of reaction is;


92 +(-1) + 2 =93

Thus, number of protons in right side of reaction must be 89.


Y+1.(0) + 2.(+1) = 93
Y=91
Y=91 number of protons

Mass number of reactants must be equal to mass numbers of products.


234+4=238 mass number of reactants
Page 8
Y+ 1.(0) + 2.(0) =238
Y =238
Y=238 mass number of Y
238
91 Y
38
37. What is the identity of X in the given reaction: 19 K → 1838Ar + X
a. -10β b. +10β
c . 24α d. -1 0e

Solution: 1938K → 1838Ar + abX


mass number and atomic numbers must be equal;
38=38+b
b=0
19=18+a
a=1 thus, +10X or +10β

38. Calculate the average molar mass of air at sea level and 0oC if the density of air is 1.29 Kg m-3.

a. 30.1 g/mol b. 32.5 g/mol


c. 28.9 g/mol d. 25.2 g/mol

Solution:
PV = nRT  P = (n/V) RT  P = (m/MW)/V (RT)  D = m/V and MW is molecular weight  P = D/ MW (RT)

MW = DRT/ P  (1.29 Kg m-3 x 8.314 J K-1 mol-1 x 273.15 K ) / 101, 325 N m-2 (or Pa) Note 1 N = Kg m s-2
MW = (1.29 Kg m-3 x 8.314 J K-1 mol-1 x 273.15 K )/ 101,325 Kg m s-2 m-2 (or Pa) = 28.9 g mol-1

39. In an industrial process, nitrogen is heated to 500 K at a constant volume of 1.00 m3. The gas enters the
container at 300 K and 100 atm. The mass of the gas is 92.4 kg. Use the van der waals equation to determine the
approximate pressure of the gas at its working temperature of 500 K. For nitrogen, a = 1.352 dm6 atm mol-1; b =
0.0387 dm3 mol-1.
a. 140 atm b. 280 atm
c. 100 atm d. 75 atm

Solution: Determine the amount of gas first. The 300 K and 100 atm are unnecessary information.
n = 92.4 kg ( 28.02 g)(1000 Kg/g) = 3.30 x10 3mol
V = 1.00 m3 = 1.0 x103 dm3
p = (nRT/ V-nb) – an2/ V2
p = [(3.30 x 103 mol) (0.08206 dm3 atm K-1mol-1) (500K))/ (1.0x103 dm3)(b = 0.0387 dm3 mol-1)] –
cont. (1.352 dm6 atm mol-1)( 3.30 x10 3mol)2/ 1.00 m3 = 1.0 x103 dm3
p = (155- 14.8 ) = 140 atm

40. Consider a volume 5.0 dm3 that is divided into two compartments of equal size. In the left compartment there
is nitrogen at 1.0 atm and 25oC; In the right compartment there is hydrogen at the same temperature and
pressure. Assume that the gasses are perfect, calculate the Gibbs energy of mixing when the partition is removed.
a. + 0.35 kJ b. +0.70 kJ
c. -0.35 kJ d. – 0.70 kJ

Solution:
G = nRT (XA ln XA + XB ln XB)  XA =XB = 0.5 n RT = pV
Therefore,
G = pV (½ ln ½ + ½ ln ½ ) = (1 atm )(1.013 x 105 Pa) (5.0 x 10-3 m3) (ln 2)
G = - 3.5 x102 J = -0.35 kJ

41. “Gobar gas” contains mainly


a. ethylene b. methane

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c. carbon monoxide d. acetylene
Solution:
Gobar gas is a biogas composed of methane. Biogas in India has been traditionally based on dairy manure as feed
stock and these "gobar" gas plants have been in operation for a long period of time, especially in rural India.

42. The first organic compound to be synthesised in the laboratory was …


a. ethylene b. acetic acid
c. methane d. urea
Solution: In 1828, Friedrich Wöhler, a German physician and chemist by training, published a paper that describes
the formation of urea, known since 1773 to be a major component of mammalian urine, by combining cyanic acid
and ammonium in vitro. In these experiments the synthesis of an organic compound from two inorganic molecules
was achieved for the first time.

43. R.A 6969 is also known as the:


a. Philippine Clean Air Act of 1999 b. Ecological Solid Waste Management Act of 2000
c. Philippine Clean Water Act of 2004 c. Toxic Substances, Hazardous and Nuclear Waste Control Act of 1990
Solution:
a. Philippine Clean Air Act of 1999- R.A 8749
b. Ecological Solid Waste Management Act of 2000 – R.A 9003
c. Philippine Clean Water Act of 2004- R.A 9275
d. Toxic Substances, Hazardous and Nuclear Waste Control Act of 1990- R.A 6969

44. The following is a structure of menthol without showing stereochemistry. How many chirality centres does
menthol have and how many stereoisomers are possible? Choose the correct combination of numbers.

a. 3 centres and 9 isomers b. 3 centres and 8 isomers


c. 3 centres and 6 isomers d. 2 centres and 4 isomers
Solution: no of isomers = 2n where n = no of chiral centres

45. In a preparation of ethene, ethanol is added a drop at a time to a heated reagent Y. To purify the ethene it is
bubbled through a solution of Z and then collected. What could be reagent Y and solution Z be?

Reagent Y Solution Z
a. Acidified K2Cr2O7 Dilute NaOH
b. Concentrated H2SO4 Dilute H2SO4
c. Concentrated H2SO4 Dilute NaOH
d. Ethanolic NaOH Concentrated H2SO4

Solution:
Conc. H2SO4 (reagent Y) is used to dehydrate ethanol to ethene: C2H5OH  CH2=CH2 + H2O
NaOH (solution Z) is used to neutralise and remove any excess conc. H2SO4 from ethene.

46. In titrimetric analysis, which of the following method-titrant pairs is NOT CORRECT?
a. Permanganimetry – KMnO4 b. Iodimetry – Na2S2O3
c. Fajans– KSCN d. Mohr – AgNO3
Solution:

Page 10
In the Volhard method for Ag+ using KSCN as the titrant, for example, a small amount of Fe3+ is added to the titrand’s
solution. The titration’s end point is the formation of the reddish-colored Fe(SCN)2+ complex. The titration must be
carried out in an acidic solution to prevent the precipitation of Fe3+ as Fe(OH)3.

In the Fajans method for Cl– using Ag+ as a titrant, for example, the anionic dye dichlorofluoroscein is added to the
titrand’s solution. Before the end point, the precipitate of AgCl has a negative surface charge due to the adsorption
of excess Cl–. Because dichlorofluoroscein also carries a negative charge, it is repelled by the precipitate and remains
in solution where it has a greenish-yellow color. After the end point, the surface of the precipitate carries a positive
surface charge due to the adsorption of excess Ag+. Dichlorofluoroscein now adsorbs to the precipitate’s surface
where its color is pink. This change in the indicator’s color signals the end point.

47. Nickel Asia is the largest nickel producer in the Philippines and you are asked to measure the Nickel (FM =
58.69 g/mol) content in steel. The alloy is dissolved in 12 M HCl and neutralized in the presence of citrate ion,
which maintains iron in the solution. The slightly basic solution is warmed, and dimethylglyoxime (DMG) is added
to quantitatively precipitate the red Ni-(DMG)2 complex. The product is filtered, washed with cold water and
dried at 110oC. If the nickel content is known to be near 3 wt% and you wish to analyze 1.0 g of steel, what volume
of 1.0 wt % DMG should be used to give 50 % excess of DMG for the analysis? Assume the density of the alcohol
solution is 0.79 g/mL.
a. 13.1 mL b. 15.3 mL
c. 23.0 mL d. 20.5 mL
SOLUTION: Because the Ni content is about 3%, 1.0 g of steel will contain about 0.03 g of Ni, which corresponds to:
0.03 g Ni / 58.69 g Ni/mol Ni = 5.11 X 10-4 mol Ni
This amount of metal requires: 2(5.11 X 10-4 mol Ni) (116.12 g DMG/mol Ni) = 0.119 g DMG
because 1 mol of Ni2+ requires 2 mol of DMG. A 50% excess of DMG would be (1.5) (0.119 g) = 0.178 g This much
DMG is contained in: 0.178 g DMG / 0.010 g DMG/g solution = 17.8 g solution
which occupies a volume of: 17.8 g solution / 0.79 g solution/mL = 23 mL

48. A drop of Na2S solution is added to 1 M AgNO3 solution. If the solubility of Ag2S is surpassed and the conditions
are ideal for colloid formation, the formula for the colloid is…..
a. Ag2S: S2-… Na+ b. Ag2S:Ag+… NO3-
c. Ag2S: Na+… S2- d. Ag2S:Na+… NO3-

49. Which cation forms a colourless aqueous solution?


2+ 2+
a. Co b. Ni
2+ 2+
c. Cu d. Zn
Solution
Co2+ (pink) ; Ni2+ (light green); 2+
Cu (blue) ;
2+
Zn (colourless)

For numbers 50 to 52 : Consider an investigation of the decomposition of N 2O5 (g) at 35oC, an initial concentration
of N2O5(g), [N2O5]0, of 0.0300 mol/L was used. The rate constant for the reaction is known to be 1.35 x10 -4/s.

50. What is will be the concentration of N2O5 (g) after 30.0 minutes?
a. 0.1175 mol/L b. 0.2350 mol/L
c. 0.0118 mo/L d. 0.0235 mol/L

Solution: convert per sec to per minute


K = (1.35 x 10-4/s) (60 s/min) = 8.10 x 10-3 min-1
Log ([N2O5]0/[N2O5]) = kt/ 2.303
Log [0.0300]/ [N2O5]) = 8.10 x 10-3 min-1 (30 minutes) / 2.303 = 0.1055
0.0300 mol/L / [N2O5] = antilog 0.1055
[N2O5] = 0.0300 mol/L / 1.275 = 0.0235 mol/L

51. How many minutes will it take for the concentration of N2O5 (g) to drop to 0.0200 mol/L?
a. 30 mins b. 40 mins
c. 50 min d. 60 mins

Solution:
Log ([N2O5]0/[N2O5]) = kt/ 2.303

Page 11
Log ([0.0300/0.0200) = 8.10 x 10-3 min-1 (t)/ 2.303
2.303log (1.50) = 8.10 x 10-3/ min (t)
t = 50.0 min

52. How many minutes will it take for 90% of the N2O5(g) to decompose?
a. 290 min b. 500 min
c. 270 min d. 284 min

Solution:
Since 90 % of the N2O5 has decomposed, [N2O5] is equal to 10.0 % of the original concentration, [N2O5]o
[N2O5] = 0.100 [N2O5]0
[N2O5] = 0.100 (0.0300) = 0.00300 mol/L  use this to substitute in part (b). Another way to solve the problem is:
[N2O5] = 0.100 [N2O5]0
[N2O5]0/[N2O5] = [N2O5]0 / 0.100 [N2O5]0
[N2O5]0/[N2O5] = 10

Log ([N2O5]0/[N2O5]) = kt / 2.303


Log (10) = 8.10 x 10-3 min-1 t / 2.303
t = 2.303 (log 10) / 8.10 x 10-3 min-1 = 284 min

53. How many sigma bonds are in 2-butyne (CH3C≡CCH3)?


a. 3 b. 6
c. 9 d. 11

Solution: a triple bond consists of 2 pi bonds and one sigma bond; C-H bonds are sigma bonds

54. How many unpaired electrons are in the superoxide ion, O2– ?
a. zero b. one
c. two d. three

Solution:

55. A six-carbon organic compound containing oxygen is suspected of being either a secondary alcohol or a
ketone. Which chemical or physical test would best distinguish between these two possibilities?
a. Water solubility b. Melting point
c. Treatment with sodium bicarbonate d. Treatment with acidic dichromate

Solution: a secondary alcohol is oxidized into a ketone by acidic dichromate.


56. A sample of 35 16S, a β- emitter, has an activity of 0.100 µCi. In 20.0 days, the activity of the sample has declined
to 0.0853 µCi. What is the half-life of 3516?
a. 80 days b. 82 days
c. 87 days d. 89 days

Solution:
Activities are expressed as number of disintegrations per second that occur in a given time interval. Curie is a
definition used. 1 curie = 1 Ci = 3.70 x1010 disintegrations per second.
Activity of the radioactive nuclide is proportional to the number of atom present. Hence. No/N is equal to the ratio
of the activity of the sample at time = 0 to the activity of the sample at time = t.
Log (No/N) = kt/ 2.303
Log (0.100 µCi / 0.0853 µCi) = k (20.0 day)/ 2.303 = k = 7.95 x10-3/ day
The half-life can be derived:
t ½ = 0.693 / k  0.693/ 7.95 x10-3/day = 87.2 days

57. The decomposition of HI (g): 2 HI (g)  H2(g) + I2(g) is a second order reaction, and the rate constant for the
reaction run at 410 oC is 5.1 x10-4 L/(mol.s). In an experiment at 410 oC, the intial concentration of HI (g) was 0.36
mol/L. What is the concentration of HI gas after 12 minutes have elapsed?
a. 0.32 mol/L b. 0. 64 mol/L

c. 0.40 mol/L d. 0.16 mol/L


Page 12
Solution: K = 5.1 x10-4 L / (mol.s)( 60 min/1sec) = 3.06 x 10-2 L / mol.min
1 / [HI] = kt + 1/ [HI]0
1 / [HI] = 3.06 x 10-2 L / mol.min (12 minutes) + 1/(0.36 mol/L)
1 / [HI] = 0.367 L/mol + 2.78 L/mol = 3.15 L/mol
[HI]= 0.32 mol/L

58. What is the nature of the peptide bonds in a protein?


a. Hydrogen bonds b. Amide bonds
c. Disulfide bonds d. Ionic bonds

59. Which two bases are found as a hydrogen-bonded base pair in DNA?
(A) A and T (B) C and T (C) C and U (D) G and U

DNA: A -T (two hydrogen bonds) G-C (three hydrogen bonds)


RNA: A-U and G-C

60. The vapour pressure of benzene is 53.3 kPa at 60.6 oC, but it fell to 51.5 kPa when 19.0 of an involatile organic
compound was dissolved in 500 g benzene. Calculate the molar mass of the compound.
a. 82 g/mol b. 93 g/mol

c. 41 g/mol d. 130 g/mol

Solution:
Assume the solvent, benzene, is ideal and obey Raoults law.
Let B denote benzene and A denote the solute
pB = XB P*B and XB = nB / nB + nA

Hence, pB = (nB / nB + nA) (P*B) which solves into


nA = nB (P*B - pB) / pB

Then, since nA = mA/MWA , where mA is the mass of A present


nB = mB/MWB
MWA = mA pB / (nB) (P*B - pB) = mA MWB pB / mB (P*B - pB)
From the data:
MWA = mA MWB pB / mB (P*B - pB)
MWA = 19.0 g (78.11 g/mol) (51.5 kPa) / 500 g (53.3 kPa – 51.5) = 82 g/mol
61. A 10.0 mL aliquot of sulfuric acid solution requires 28.16 mL of 0.1000 M sodium hydroxide for titration. What
volume of 0.1000 M BaCl2 will be required to titrate a second 10.0 – mL aliquot of the H2SO4 solution id BaSO4 is
precipitated?
a. 14.1 mL b. 15.0 mL
c. 13.5 mL d. 28.5 mL

Solution:
(28.16 mL) (0.1000 mmol/mL NaOH ) (1 mmol H2SO4/2 mmol NaOH) = 1.408 mmol H2SO4
VBaCl2 (M BaCl2) = mmol H2SO4 (1:1 ratio)
VBaCl2 (0.100 mmol/mL) = 1.408 mmol H2SO4
VBaCl2 = 14.08 mL

62. Which molecule is nonpolar, yet contains polar covalent bonds?


a. CO2 b. HCN
c. NH3 d. P4

63. Calculate the percentage iodide (At. Wt. 126.9) in a 1.000 g sample to which is added with an excess of 50.00
mL of 0.1000 M AgNO3. The unreacted Ag NO3 is then back-titrated with 16.00 mL 0f 0.0800 M KSCN, producing
AgSCN(s).
a. 23.5 % b. 47.21%
c. 94.2 % d. 50.5 %

Page 13
Solution:
[(50.00 mL) (0.1000 mmol/mL AgNO3) – (16.00 mL)(0.0800mmol/mL KSCN) (1/1) (126.9 g/mol) ]/ 1000.0 mg
% iodide = 47.21 %

64. A 25.00-mL sample containing Fe3+ and Cu2+ required 16.06 mL of 0.050 83 M EDTA for complete titration. A
50.00-mL sample of the unknown was treated with NH4F to protect the Fe3+. Then Cu2+ was reduced and masked
by thiourea. Addition of 25.00 mL of 0.050 83 M EDTA liberated Fe3+ from its fluoride complex to form an EDTA
complex. The excess EDTA required 19.77 mL of 0.018 83 M Pb2+ to reach a xylenol orange end point. Find molar
concentration of Cu2+ in the unknown sample.
a. 0.10 M b. 0.25 M
c. 0.15 M d. 0.30 M

Solution:
In 25.0 mL : mmol Fe 3+ + mmol Cu 2+ = (16.06 mL x 0.05083 mmol/ mL) = 0.816 3 mmol.

Second Titration:
millimoles EDTA used: [(35.00 mL)(0.05083 mmol/mL) - (19.77 mL)( 0.01883 mmol/mL) (1/1)] = 0.8985 mmol
millimoles EDTA = millimoles Fe3+ (present) = 0.08985 mmol
Because 50.00 mL of unknown were used in the second titration,
0.8985 mmol (25/50) = 0.4492 mmol Fe3+(in the original 25 mL)

The millimoles of Cu2+ in 25.00 mL are 0.816 3 - 0.449 2 = 0.3671 mmol/25.00 mL = 0.014 68 M = 0.15 M

65. Which simple chemical test / reagent will differentiate cumene from styrene?
a. Br2, CH2Cl2 b. Br2, FeBr3 c. Tollens test d. Benedict’s Test

Solution:
Cumene is also known as isopropyl benzene and styrene is vinyl benzene. Choice A will react with the vinyl group of
benzene.

66. The rate of diffusion of a volatile monoprotic organic acid from container A into container B, which contains
2.00 mL of 0.8040 M potassium hydroxide, is being measured. After 2 hours, the acid in A required 1.53 mL of
0.0100 M sodium hydroxide for titration; the excess potassium hydroxide in B requires 1.90 mL of 0.2000 M HCl
for titration. Calculate the percentage of organic acid that has diffused into container B.
a. 98.8 % b. 92.3 %
c. 89.9 % d. 96.0%

Solution:
Calculate the amount of organic acid in each container
Container A: 1.53 x 0.0100 = 0.0153 mmol
Container B: [(2.00 mL) (0.8040 mmol/mL)] – [(1.90 mL) (0.200 mmol/mL)] = 1.228 mmol
Percent diffused = (1.228 / 1.228 + 0.0153) 100 = 98.77 %

67. The concentration of CO2 (FM = 44) in air in Metro Manila was determined by an indirect acid–base titration. A
sample of the air is bubbled through a solution containing an excess of Ba(OH) 2, precipitating BaCO3. The excess
Ba(OH)2 is back titrated with HCl. In a typical analysis, a 3.50-L sample of air was bubbled through 50.00 mL of
0.0200 M Ba(OH)2. Back titrating with 0.0316 M HCl requires 38.58 mL to reach the end-point. Determine the parts
per million of CO2 in the sample of air, given that the density of CO2 at the temperature of the sample is 1.98 g/L.
a. 3000 ppm b. 2479 ppm
c. 2234 ppm d. 2998 ppm

Solution:
Reaction 1: Ba(OH)2 + 2HCl -> BaCl2 + 2H2O
mmoles Ba(OH)2 = [(50.00 mL) (0.0200 mmol/mL) –(0.0316 mmol/L)(38.58 mL HCl) (1/2)] = 0.3904 mmol Ba(OH)2
Reaction 2: Ba(OH)2 + CO2 -> BaCO3 + H2O
{[0.3904 mmol Ba(OH)2 (1 mmol CO2 / 1 mmol Ba(OH)2) (1 mol/1000 mmol) (44 g/mol) (1/1.98 g/L) ] 3.50 L} x 10 6 =
2479 ppm

Page 14
68. A 0.9092 g sample of wheat flour was analyzed by the Kjeldahl procedure. The ammonia formed was distilled
into 50.00 mL of 0.05063 M HCl; a 7.46 mL back titration with 0.04917 M NaOH was required. Calculate the
percent protein in the flour. (Gravimetric Factor for this protein wrt wheat is 5.70).
a. 21.2 % b. 25.1 %
c. 19.0 % d. 15.7 %

Solution:
Moles of acid consumed = Moles originally present – moles excess
Originally present = 50.00 x 0.05063 = 2.5315 mmol
Excess = 7.46 x 0.04917 = 0.3668 mmol NaOH = mol HCl
Net mmol HCl = 2.5315 – 0.3668 = 2.1647 mmol consumed
Amount N = 2.1647 mmol acid = 2.1647 mmol N
Weight N = 2.1647 mmol N x 14.0067 mg/mmol = 30.32 mg N
Mass of protein 30.32 mg N x 5.70 = 172.8 mg protein
% protein = (172.8 mg p / 909.2 mg s) x 100% = 19.0% protein

69. A compound with the formula C6H12 does not decolorize bromine in CHCl3 solution. Which compound could
this be?
a. Cyclohexane b. 1-Hexene
c. Trans-3-hexene d. Cis-3-hexene

70. The net chemical reaction of photosynthesis is best described as…


a. an endothermic reaction that forms sugars b. an endothermic reaction that breaks down sugars
c. an exothermic reaction that forms sugars d. an exothermic reaction that breaks down sugars

71. A secondary effluent has a total BOD5 of 45 mg/L. A BOD5 test is run on this same secondary effluent at the
same time using a nitrification “inhibitor”. Using the data for this test as give below, calculate the nitrogenous
BOD. Assume a 300 mL BOD bottle is used to run this test.

Sample Size: 30 mL 50 mL Blank


Initial DO, mg/L 8.9 8.8 9.0
Final DO, mg/L 6.0 4.2 8.9

a. 16.7 mg/mL b. 15.2 mg/mL


c. 10.4 mg/mL d. 18.5 mg/mL

Solution:
Total BOD = carbonaceous BOD (CBOD) + nitrogenous BOD (NBOD)
 use nitrification inhibitor means were calculating for carbonaceous BOD
BOD mg/L = [(8.9-6.0) x 300mL]/30 mL = 29 mg/L
BOD mg/L = [(8.8-4.2) x 300mL]/30 mL = 27.6 mg/L
Average BOD = (29 mg/mL + 27.6 mg/mL)/ 2 = 28.3 mg/L
NBOD = Total BOD – CBOD = 45 mg/mL – 28.3 = 16.7 mg/mL

For items 72 – 73: Consider a sample of 4.50 g of methane (FM = 16.04) occupies 12.7 dm3 at 310 K

72. Calculate the work done when the gas expands isothermally against a constant external pressure of 200 Torr
until its volume has increased by 3.3 dm3.
a. + 88 J b. – 88 J
c. + 660 J d. – 660 J

Page 15
Solution:
w = -p ext V (expansion work against constant external pressure)
pext = (200 Torr) (133.3 Pa / Torr) = 2.666 x 104 Pa
V = 3.3 dm3 = 3.3 x 10-3 m3
Therefore, w = -(2.666 x 104 Pa) (3.3 x 10-3 m3) = - 88J

73. Calculate the work that would be done if the same expansion occurred reversibly.
a. + 167 J b. – 167 J
c. + 84 J d. – 84 J

Solution:
w= - nRT ln (Vf/Vi) (work done by perfect gas at reversible isothermal expansion)
n = 4.50 g / 16.04 = 0.2805 mol; RT = 2.577 kJ mol-1, Vi = 12.7 dm3, Vf = (12.7 + 3.3 ) = 16.0 dm3
w = - (0.2805 mol) (2.577 kJ mol-1) ln ( 16.0 dm3/12.7 dm3) =- 0.1669 kJ = -167 J

74. A sample of wastewater has an ultimate BOD of 280mg/L and a 5‐day BOD of 240mg/L. Calculate 20‐day BOD
of this sample.
a. 179.9 mg/L b. 165 mg/L
c. 279.9 mg/L d. 230 mg/L

Solution:
y20 = L0 (1 ‐ e‐k*20):
First calculate k using given data: y5 = L0 (1 ‐ e‐k*5)  240 = 280 (1 ‐ e‐k*5)  k = 0.39 d‐1
Then, 20‐day BOD: y20 = L0 (1 ‐ e‐k*20) = 280 (1 ‐ e‐0.39*20) = 279.9 mg/L

75. Which is least reactive in electrophilic substitution?


a. b. c. d.

76. Calculate the final temperature of a sample of argon of mass 12.0 g that is expanded reversibly and
adiabatically from 1.0 dm3 at 273.15 K to 3.0 dm3. The molar heat capacity (Cp,m) for argon is 20.786.
a. 120 K b. 135 K
c. 115 K d. 131 K

Solution:
For a reversible adiabatic expansion:
Tf = Ti (Vi/Vf) 1/c

Where c = CV,m /R and Cp,m - Cv,m = R (relation between heat capacities of perfect gas)
Therefore, c = (Cp,m – R) / R (Note: Cp,m heat capacity at constant pressure ; Cv,m heat capacity at constant volume)
Note Cp,m = a + bT + C/ T2  temperature variation of molar heat capacity  for all monoatomic gas = 20.78.

c = (Cp,m – R) / R = (20.786 – 8.314 ) J K-1 mol-1 / 8.314 J K-1 mol-1 = 1.500


final temperature is :
Tf = 273.15 K (1.0 dm3 / 3.0 dm3)1/1.500 = 131 K

77. This is an esterification reaction, butyric acid reacts with ethanol to form ethyl butyrate

78. A sample of carbon dioxide of mass 2.45 g at 27oC can expand reversibly and adiabatically from 500 cm3 to
3.00 dm3. What is the work done by the gas? The molar heat capacity at constant pressure for carbon dioxide is
37.11 J k-1 mol-1
a. 200 J b. 240 J
c. -197 J d. 134 J

Page 16
Solution:
Reversible adiabatic work is : w = CV T = n (Cp,m - R) (Tf-Ti)
Calculate the Tf using the formula:
Tf = Ti (Vi/Vf) 1/c where c = (Cp,m – R) / R = (37.11 – 8.314 ) J K-1 mol-1 / 8.314 J K-1 mol-1 = 3 .46

Therefore, Tf = 300 K (500 x 10-3 dm3/3.00 dm3) 1/3.46 = 179 K


Finally, work is calculated: w = (2.45g/44.0 gmol-1)(37.11-8.314)J K-1 mol-1 (179 K – 300 K) = -197 J

For items no 79 to 80: When 229 J of energy is supplied as heat to 3.0 mol Ar (g) at constant pressure, the
temperature of the sample increases by 2.55 K.

79. What is the molar heat capacity at constant pressure.


a. 20 K-1 mol-1 b. 30 K-1 mol-1
c. 25 K-1 mol-1 d. 35 K-1 mol-1

Solution:
Cp = qp/T = 229 J / 2.55 K = 89.8 J K-1
Therefore, Cp,m = 89.8 J K-1 / 3.0 mol = 30 J K-1 mol-1

80. What is the molar heat capacity at constant volume.


a. 12 K-1 mol-1 b. 17 K-1 mol-1
c. 22 J K-1 mol-1 d. 27 K-1 mol-1

Solution:
For a perfect gas : Cp,m - Cv,m = R
Therefore, Cv,m = Cp,m- R  (30 -8.31 J K-1 mol-1) = 22 J K-1 mol-1

81. What is the standard molar entropy of a constant-volume sample of neon at 500 K given that it is 146.22 J K-1
mol-1 at 298 K. Assume that Neon is a perfect gas.
a. 152.7 J K-1 mol-1 b. 170.8 J K-1 mol-1
c. 160.5 J K-1 mol-1 d. 190.9 J K-1 mol-1

Solution:
Entropy variation with temperature: Sm (Tf) = Sm (Ti) + ʃ Tf Ti Cv,m/T dT (relplace Cp,m with Cv,m)
Integrating: Sm (Tf) = Sm (Ti) + Cv,m ln Tf/Ti
Note: for a perfect gas Cv,m = Cp,m – R and for monoatomic gas Cp,m = 20.786 J K-1 mol-1
CV,m = (20.786 – 8.314 ) J K-1 mol-1 = 12.472 J K-1 mol-1
Finally,
Sm (500 K) = Sm (298 K) + 12.472 J K-1 mol-1 ln (500 K /298K) =
Sm (500 K) = 146.22 J K-1 mol-1 + 12.472 J K-1 mol-1 ln (500 K /298K) = 152.67 J K-1 mol-1

82. For the complete combustion of ethanol: C2H5OH(l) + 3 O2 (g)  2 CO2(g) + 3 H2O(l)
The amount of heat produced, as measured in a bomb calorimeter, is 1364.47 kJ mol-1 at 25oC. What is the H for
the reaction? Assume ideal gas law applies to the system.
a. -2457.8 kJ mol-1 b. – 4563.4 kJ mol-1

c. -3167.0 kJ mol-1 d. -1366.9 kJ mol-1

Note: calorimeters constant volume  change in internal energy U


Calorimeters constant pressure  change in enthalpy H
Relationship: H = U +  (PV) Assume ideal gas law applies to the system.
PV = nRT therefore,  (PV) =  ng (RT)
Therefore, H = U +  ng (RT)

Since the bomb calorimeter prates at constant volume then, U = - 1364.47 kJ mol-1. The product contains 2 mol of
gas and 3 mols of gas in the reactant, thus,  ng = 2-3 = -1. Thus,

Page 17
H = - 1364.47 kJ mol-1 + (-1 mol) (8.314 J mol-1K-1) (298.15 K) (1 kJ / 1000J) = -1366.95 kJ mol-1

83. 8.278 x 10¯4 mol of an unidentified gaseous substance effuses through a tiny hole in 86.9 s Under identical
conditions, 1.740 x 10¯4 mol of argon gas takes 81.3 s to effuse. What is the molecular formula of the substance?
a. H2 b. He
c. CH4 d. Ne

Solution:
Calculate the rates of effusion:
unknown ⇒ 8.278 x 10¯4 mol / 86.9 s = 9.525892 x 10¯6 mol/s
argon ⇒ 1.740 x 10¯4 / 81.3 s = 2.140221 x 10¯6 mol/s
Note that these are not speeds. A speed is an amount of distance covered in a unit amount of time. The above is a
rate, several moles of gas effuse through a pinhole in a unit amount of time.

2) Use Graham's Law: r1 / r2 = MM2 / MM 1


Assign the unknown molar mass to be MM2. I will cancel the exponent on the rates, since they are both 10¯6.
2.140221 / 9.525892 = MM2 / 39.948

3) Solve: 0.05047844 = MM2 / 39.948


MM2 = 2.0165 g/mol (the answer to part a)
The gas is hydrogen, H2 (the answer to part b; no other gas weighs 2).

84. Which amino acid is NOT involved in the building of proteins in the body?
a. H2NCH(CH2C6H5)CO2H b.HO2CCH(NH2)CH3
c. H2NCH(CO2H)CH2CONH2 d. HO2CCH2CH(CH3)NH2

Solution: Proteins in the body are built from 2-aminocarboxylic acid (or alpha-amino carboxylic acid)
Letter D is a 3-amino carboxylic acid

85. What is the boiling point of water at 98.7 kPa (approximately 740 Torr, a typical barometric pressure at 275 m)
?. The heat of vaporisation is 2258 J g-1, the molar volume of liquid water is 0.019 dm3 mol-1, and the molar volume
of steam is 30.1999 dm3 mol-1, all values referring to 373.1 K and 101.325 kPa (1 atm).
a. 372.42 K b. 370.34 K
c. 300.34 K d. 380.3 K

Solution:
Clapyeron Equation: dP/dT = Hm / TVm (Use Clapeyron equation for vaporization, sublimation, fusion, or solid
phase transition of a pure substance).

Apply the equation to find the change in the boiling point for 1 Pa and hen multiply by the difference between the
given pressure and the standard atmosphere.

dP/dT = Hm / T (Vm (vapor) - Vm (liquid)


dP/dT = 2258 J g-1 (18.01 8 mol-1) / [(373.1K) x ((30.1999 dm3 mol-1) - (0.019 dm3 mol-1)]
dP/dT = 3.614 J K-1 dm-3 = 3.614 x 103 J m-3 K-1
dP/dT = 3.614 x 103 Pa K-1= 3.614 kPa K-1
or
dT/dP = 2.77 x10-4 K Pa-1

For a decrease of 101.325 – 98.7 kPa = 2.625 kPa =2625 Pa, there is a decrease in temperature of

2.77 x10-4 K Pa-1 (2625 Pa) = 0.73K


Therefore, the new boiling point is 373.15 K – 0.73 K = 372.42K
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86. Which naturally occurring α-amino acid is achiral?
a. Glycine b. Glutamine
c. Leucine d. Serine

87. Benzene has a normal boiling point at 760 Torr 353.25 K and vapHm = 30.76 kJ mol-1. If Benzene is to be boiled
at 300oC in vacuum distillation, to what value of P must the pressure be lowered?
a. 200.0 Torr b. 124. Torr
c. 145.2 Torr d. 134.6 Torr

Solution:
In order to boil benzene its vapour pressure must equal the pressure on the system. The problem is thus a matter of
finding the vapor pressure of benzene at 300oC. We may use the Clausius-Clapeyron Equation considering vapHm
constant over the temperature range. T2/K = 300.00 oC /oC + 273.15 = 303.15 K

Clausius – Clapeyron Equation:

ln P2/P1 = vapHm / R (1/T1 – 1/T2)


ln P2/760.0 = 30.76 kJ mol-1/8.314 J mol-1 K-1 (1/353.25 – 1/303.15)
ln P2/760.0 = -1.7309
ln P2 = 4.9024; P2 = 134.6 Torr

88. Estimate the enthalpy of vaporization of CS2 if its boiling point is 319.40 K.
a. 27.15 kJ mol-1 b. 40.5 kJ mol-1
c. 30.1 kJ mol-1 d. 32.4 kJ mol-1

Solution: Apply Troutons ( for non- hydrogen bonded compounds)


vapHm / Tb = vapSm = 85 J K-1 mol-1
vapHm = vapSm x Tb
vapHm = 85 J K-1 mol-1 x 319.40 K =27149 J mol-1 = 27.15 kJ mol-1

89. On average, carbon dioxide travels at 410 m/s at 25 °C. Find the average rate of chlorine at 25°C?
a. 400 m/s b. 250 m.s
c. 304 m/s d. 320 m/s

Solution:
Gas 1= CO2; Rate CO2= 410 m/s
Gas 2= Cl2 ; Rate Cl2= ? m/s

Grahams Law of Effusion: Rate 1 / Rate 2 = √molecular mass 2 / √molecular mass 1


410 ms-1 / Rate Cl2 = √ 71.0 / √ 44.0
Rate Cl2 = 410 m/s (√ 44.0)/ √ 71.0 = 320 m/s

90. You need to prepare an acetate buffer of pH 6.420 from a 0.664 M acetic acid solution and a 2.50 M KOH
solution. If you have 975 mL of the acetic acid solution, how many milliliters of the KOH solution do you need to add
to make a buffer of pH 6.42? The pKa of acetic acid is 4.752.

a. 254 mL b. 250 mL
c. 314 mL d. 300 mL

Solution:
1) Moles of acetic acid:
(0.664 mol/L) (0.975 L) = 0.6474 mol
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2) Henderson-Hasselbalch Equation:
pH = pKa + log [base / acid]
6.420 = 4.752 + log [x / (0.6474 − x)]
The x is the moles of acetate that must be present and the 0.6474 − x is the amount of acetic acid.

3) Algebra!
log [x / (0.6474 − x)] = 1.668
[x / (0.6474 − x)] = 46.5586
x = 30.142 − 46.5586x
47.5586x = 30.142
x = 0.63379 mol
Acetate and KOH are in a 1:1 stoichiometric ratio, so this is the required number of moles of KOH.

4) Volume of KOH needed:


0.63379 mol / 2.50 mol/L = 0.253516 L
254 mL seems like a reasonable answer

5) We can try our calculated values and see what happens:


pH = 4.752 + log (0.63379 / 0.01361) = 6.420

91. Which Group 17 element has the least attraction for electrons?
a. F b. Cl c. Br d. I

92. Which element has the greatest tendency to gain electrons?


a. Te b. Se c. S d. O

93. Which sequence correctly places the elements in order of increasing ionization energy?
a. H Li  Na  K b. O SSe  Te
c. I  Br Cl  F d. H Be  Al  Ga

94. The only natural amino acid that has no chiral centre is:
a. Cysteine b. Proline b. Tryptophan d. Glycine

95. The purpose of control rods in a fission reactor is to:


a. cool down the reactor fuel. c. absorb neutrons generated in the fission process.
b. prevent oxygen from reaching the fuel. d. absorb electrons emitted in the fission process.

96. 2-Methyl-2-butene undergoes hydrochlorination in the presence of benzoyl peroxide to form:


a. 3-Chloro-3-methylbutane c. 2-Chloro-3-methylbutane
b. 2-Chloro-2-methylbutane d. 1-Chloro-3-methylbutane

97. Treatment of 1.200-g sample of an impure potassium chloride with an excess AgNO3 resulted in the formation of
0.2563 g AgCl. Calculate the percentage of KCl in the sample.
a. 86.02% c. 67.77%
b. 49.76% d. 11.11%

98. It is an unusual state of matter, created at temperatures near absolute zero, in which a very large atom contains
other ordinary atoms in the space between the nucleus and the electrons.
a. Bose-Einstein condensate b. Rydberg polaron c. Superfluid d. Plasma

99. By heating, 1,2-elimination of 3-hexanol would yield:


a. 2,3-Hexanediol b. 3-Hexene c. n-Hexane d. 2-Hexene

100. 2,6-Diaminohexanoic acid refers to which amino acid?


a. Glutamine b. Lysine c. Leucine d. Serine

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