Pool3 Questions_Chemical Kinetics and Spectroscopy

1. logk versus 1/T graph was plotted to calculate the activation energy of a reaction using Arrhenius
equation for the effect of temperature on reaction rate. The slope of the straight line was found to be -
2.55 x 104. Calculate the activation energy of the reaction.
Ans: 4.88 × 105 Joules
2. The rate constants for the reactions are 1.6  10-3 s-1 and 1.625 10-2 s-1 at 10 °C and 30 °C respectively.
Calculate the activation energy in calories per mole.
Ans: 19750 cal/mol
3. The activation energy of a reaction is 94.14 KJ/mol, and the value of the rate constant at 40º C is 1.8 ×
10-1 sec-1. Calculate the frequency factor A.
Ans: 9.194×1010 sec-1
4. The initial concentration of N2O5 in the first order reaction N2O5 → 2NO2 + ½O2 was 1.24 × 10-2 mol
L-1 at 318 K. The concentration of N2O5 after 60 minutes was 0.20 × 10-2 mol L-1. Calculate the rate
constant of the reaction at 318 K.
Ans: 0.0304 min-1
5. A first order reaction, A → products, has a rate of reaction of 0.00250 M s–1 when [A] = 0.484 M. What
is the rate constant, k, for this reaction?
Ans: 5.17×10–3 s–1
6. For the following decomposition reaction of N2O5,

The suggested mechanism is:

Using steady state approximation for the intermediates, deduce the rate law and find the order, for the
decomposition reaction of N2O5.
7. Aqueous solution of compound A of molar mass 350 g mol-1 was prepared by dissolving 17.5 mg in
250 cm3 of water, and a sample was transferred to a cell of length 1.05 cm. The absorbance was
measured as 0.8.
(a) Calculate the molar absorption coefficient. (b) Calculate the transmittance, expressed as a
percentage, for a solution of twice the concentration.
Ans: 3800 mol-1dm3cm-1, T = 0.025 or 2.5%

8. The molar absorption coefficients of two substances, A and B, at two wavelengths (denoted 1 and 2)
are as follows: εA1= 12.0 dm3mol-1cm-1, εB1= 16.0 dm3mol-1cm-1, εA2= 21.0 dm3mol-1cm-1, εB2= 14.0
dm3mol-1cm-1.
The total absorbance of a solution at these two wavelengths in a cell of length 2.0 mm was measured as
1.6 and 2.4, respectively. What are the molar concentrations of A and B in the solution?
Ans: cA=0.48, cB=0.14
9. A solution of 3.50 g/L of compound Y in a 1.20 cm cuvette has an absorbance of 0.972 at λ max of 235
nm. Calculate the molar absorption coefficient (ε) for compound Y. Molar mass of Y = 150.0 g/mol.
Ans: 35.21 mol-1dm3cm-1
10. The absorption coefficient of a glycogen-iodine mixture is 0.25 at a light of 450 nm. What is the
concentration when the transmission is 50% in a cuvette of 1 cm?
Ans: 1.204
11. There is a substance in a solution (4 g/litre). The length of the cuvette is 2 cm, and only 50% of the
certain light beam is transmitted. What is the molar extinction coefficient if the molecular weight of the
substance is 100? How much is the beam of light transmitted when the solution is 8 g/litre? 3.76 mol-
1
dm3cm-1 and 25%
12. If a 1.53 x 10-5 M solution has an absorbance of 0.426 in a 1.00 cm cell when measured at a wavelength
of 254 nm, what is the molar absorptivity/molar extinction coefficient of the compound?
Ans: 2.78 x 104 mol-1dm3cm-1
13. Calculate the energies corresponding to the absorption maxima in (i) KMnO4, λmax = 520 nm; (ii)
chlorophyll b, λmax = 456 nm; (iii) butanone, λmax = 273 nm.
Ans: (i) 38.1 x 10-20 J (ii) 43.5 x 10-20 J (iii) 72.7 x 10-20 J
14. The fundamental vibration wavenumber of 1H35Cl is 2988.9 cm-1. Calculate the force constant (in SI
units) of the H–Cl bond. And calculate the fundamental vibration wavenumber (in cm-1) for 2H35Cl,
assuming the force constant is the same for both 1H35Cl and 2H35Cl.
Ans: 1H35Cl = 515.6 Nm-1, 2H35Cl = 2144 cm-1
15. In the far infrared spectrum of 39K35Cl an intense line is observed at 378.0 cm-1. Calculate the force
constant (in Nm-1), zero-point energy (in Joules), separation between fourth and fifth vibrational levels,
and the period of vibration of 39K35Cl.
Ans: k = 155.626 Nm-1, ZPE = 3.76 x 10-21 J, T = 8.82 x 10 –14 s
16. Which of the following molecules give vibrational absorption spectra?
(a) N2, (b) O2, (c) NO, (d) CH, (e) CO, (f) CO2, and (g) SO2
Ans: N₂ and O₂: No vibrational absorption spectrum. NO, CH, CO, CO₂, and SO₂: Gives a
vibrational absorption spectrum.
17. How many vibrational active mode(s) could be observed for the following compounds-
(a) CO2 (b) NH3 (c) H2O2
Ans: (a) 3, (b) 6, (c) 6
18. State whether the following compounds can be distinguished from their IR spectra. Give reason(s)
(a) C6H5-CH2-NH2, C6H5-CO-NH2
(b) CH3-CO-CH3, CH3CHO
(c) CH3-NH2, (CH3)2-NH
(d) CH3-CH2-O-CH2-CH3, CH3-O-CH2-CH3
Ans: (a) yes, C=O stretch. (b) yes, additional C-H stretching at ~2750 cm-1 & 2850 cm-1 (c) yes,
two N-H stretching (symmetric and asymmetric) for CH3NH2 and one for (CH3)2NH (d) no.
19. The increasing order of carbonyl stretching frequency in the following molecules is

Ans: c>b>a>d
20. A) An organic compound has molecular formula C5H10O. Deduce the structure of the compound from
the following spectral data. Assign 1H NMR peaks and the selected IR lines to the deduced structure.
IR peaks (in cm-1): 2964, 2878, 1716, 1412, 1365, 1170, 962
1
H NMR: δ 0.92(3H, triplet), 1.61(2H, sextet), 2.13(3H, singlet), 2.41(2H, triplet)
B) An organic compound has molecular formula C4H8O2. Deduce the structure of the compound from
the following spectral data. Assign the 1H NMR peaks and the selected IR lines to the deduced structure.
IR peaks (in cm-1): 2986, 2955, 1743, 1437, 1358, 1203, 1086, 1022, 964, 848
1
H NMR: δ 1.15(3H, triplet), 2.33(2H, quartet), 3.67(3H, singlet)
C)14N has nuclear spin of 1 and nuclear g factor of 0.404. Calculate the energies of the nuclear spin
states in a magnetic field of 11.50 T.
 Ans: A) B) C) -2.35 x 10-26 J, 0, +2.35 x 10-26 J
21. A) CH3-O-CHO shows two 1H NMR peaks at 480 Hz and 230 Hz, using a 60MHz spectrometer. (i)
Predict the intensity ratio of the peaks. (ii) Estimate the difference in chemical shifts for the hydrogen
nuclei. (iii) What will the separation in Hz between the two signals on a 270 MHz spectrometer be?
B) Predict the multiplicities of the signals in the 1H NMR spectra of (i) 1,1-dichloro-2,2-dibromoethane
(ii) 1,1-dichloro-2-cyanoethane (iii) 1,1-dichloroethane (iv) 2-chloropropanoic acid (ignore COOH
proton) and (v) 1,3-dichloropropane
C) An organic compound has molecular formula C9H11Br. Deduce the structure of the compound from
the following 1H NMR data. Assign the 1H NMR peaks to the deduced structure. 1H NMR (δ): 7.35
(2H, doublet), 7 (2H, doublet), 3.1 (1H, septet), 1.3 (6H, doublet).
Ans: A) i) 1:3 ii) 4.2 iii) 1125 Hz B) i) doublet, doublet (ii) triplet, doublet iii) quartet, doublet iv)
quintet, triplet v) triplet, triplet C) structure is in the below

22. A) A compound ‘X’ of mass 113 contains 21.3% carbon, 1.78% hydrogen, and 62.8% chlorine. This
compound exhibited a doublet at 284 cm-1 and 2745 cm-1 in its IR spectrum. PMR spectrum of this
compound is δ(ppm): 6.3(doublet), 9.7(doublet).
Deduce the structure of ‘X’ based on the above data with proper justification.
B) A compound ‘Y’ of molecular formula (C4H8O2) gives a strong IR peak at 1720 cm-1. The 1H NMR
spectrum is δ(ppm): 2.1(3H, singlet), 3.5(3H, singlet), 3.9(2H, singlet). What is the structure of Y?
C) Calculate the energy difference between the lowest and highest nuclear spin states of a 14N nucleus
(g = 0.4036) in a magnetic field of 15T.
D) What is the frequency shift of the resonance from TMS of a group of protons with δ = 6.33 in a
polypeptide in a spectrometer operating frequency at 500.0 MHz?
E) Give the number of 1H NMR signals and its spin-spin splitting pattern with the intensity ratio for
(CH3CH2)2O.
F) A low melting organic compound has molecular formula C3H8O4. Deduce the structure of the
compound from the following spectral data. Assign the 1H NMR peaks and selected IR bands to the
deduced structure.
IR peaks (cm-1): 3300-2500(broad), 1735, 1718, 1370, 1230, 1200, 1180, 1150, 1050
1
H NMR: δ 2.52(2H, triplet), 2.62 (2H, triplet), 3.7 (3H, singlet) and 10.4 (1H, singlet)

Ans: A) X = B) Y = C) 6.116 X 10-26 J D) 3165 Hz E)

F)
1735 (ester), 1718 (acid), OH absorption at 3000-3300 corresponds to -COOH,1050-1380: ester C-
O (Finger print region), 10.4 (1H, s)-COOH proton, 2 triplets (-CH2-CH2- protons), 3.7 (3H, s)
represents deshielded isolated -OCH3 group.
23. A) Calculate the difference in population between α and 𝛽 spin states of proton nuclei present in a
magnetic field of 14.1 T at 300K. Consider total number of nuclei are 106.
B) An organic compound has a molecular formula of C5H8Br2O. In IR, the compound shows an intense
peak at 1760 cm-1. The 1H NMR chemical shift details of the same compound are as follows. 1H NMR
(δ): 2.08(quartet, 2H), 2.4(triplet, 2H), 1.8(doublet,3H), 3.6(sextet,1H). Deduce the structure of the
compound and then assign the NMR peaks to the deduced structure.
C) Predict the number of 1H NMR signals in trans-1,2-dichloroethane.
D) Write the 1H NMR chemical shift (δ) values of the methane, ethylene, and acetylene protons in
decreasing order. Justify your answer briefly. (Pictorial representation is NOT needed).
E) A compound with molecular formula C9H10 shows IR peaks at 3089, 2945, 1463, 1500-1400 and
900-675 cm-1. The NMR peaks appear at δ 2.12 [quintet (i.e. multiplicity 5), 2H], 2.90(t, 4H), 7.01-7.30
(multiplet, 4H). Deduce the structure of the compound with the proper assignment of the NMR signals.

Ans: A) 48 B) C)1 D) Methane<acetylene<ethylene. This trend can be justified

partially by the percent s- character of the carbons involved, which is related to its
electronegativity. However, only the diamagnetic anisotropy effect can explain why the protons
in acetylene have chemical shifts less (upfield) than ethylene. E) structure is in the below

24. A) Draw the structure of TMS, indicate its application in NMR spectroscopy. Calculate the precessional
frequency of 1H in TMS under the magnetic field 8T.
B) The molecular formula of two isomers is C4H8O2. When NMR spectra were collected in a 300 MHz
1
H NMR instrument using CDCl3 solvent, the isomer I shows the following 1H NMR spectrum: δ
1.25(3H, triplet), 2.03(3H, singlet) and 4.12 (2H, quartet). The isomer II, however, shows the following
spectrum: δ 1.15 (3H, triplet), 2.35(2H, quartet), and 3.69 (3H, singlet). Determine the double bond
equivalence and structures of both the isomers with proper assignments.
C) An organic compound has the molecular formula C4H7BrO2. Deduce the structure of the compound
from the following spectral data. Assign the 1H NMR peaks to the deduced structure.
IR (cm-1): 1714, 3400 (broad peak)
1
H NMR (δ): 12.0(1H, singlet), 4.3(1H, triplet), 2.2(2H, pentet), 1.2(3H, triplet)
D) How many sets of signals will be observed in 1H NMR for the compound CH2=C(OMe)(Me)?

Ans: A) Si(CH3)4, 85.7 MHz, B) D.B.E=1, ,

C) CH3CH2CHBrCO2H, D) 4
25. A) Suggest the structure for the product (X) of the following reaction, interpreting spectroscopic data.
(Label each signal in 1H NMR).

1
H NMR: δ 1.21(6H, d, J = 7Hz), 2.83(1H, septet, J = 7Hz), 3.72(3H, s), 6.74(2H, d, J = 9Hz), and
7.18(2H, d, J = 9Hz).
 B) Write the number of signals you will see in the 1H NMR spectrum of the sodium salt of
cyclopentadiene. Justify your answer.

Ans: A) X = B) Cyclopentadiene anion is aromatic Huckel’s rule (4n+2)π rule, so all

the protons are equivalent thus we see only one peak in 1H NMR spectrum.
26. A) How do you distinguish the following compounds using 1H NMR spectroscopy: CH3OCH3 and
CH3OCH2CH3.
B) Draw the structure of the following compounds, which meets the given requirements explaining
every signal given: 1H NMR spectrum of an organic compound C4H8O2 exhibits one quartet, one triplet,
and one singlet.
C) Calculate the chemical shift in ppm for a proton that has a resonance shift of 168 Hz downfield from
TMS on a spectrometer operates at 100 MHz? What should be its position both in Hz and δ (ppm) for
a spectrometer operating at 300 MHz?
Ans: A) Dimethyl ether exhibits only one peak as a singlet, whereas ethyl methyl ether exhibits
three peaks- singlet, quartet, triplet in the PMR spectrum. B) Since the compound has triplet and
a quartet it indicates the presence of Et group, It has a singlet and two oxygen atoms indicating
the presence of acetate group hence the structure is CH3COOCH2CH3. C) 1.68 x 106 ppm, 504 Hz.
27. A) The molecular formula of an organic compound is C4H8O2. The compound gives notable IR
absorption peaks at 1730 cm-1, 1200 cm-1, and 1150 cm-1. When NMR spectra is collected in a 300 MHz
1
H NMR instrument using CDCl3 solvent, the compound shows the following 1H NMR spectrum: δ
(ppm): 0.98 (3H, triplet), 1.7(2H, sextet), 4.12(2H, triplet) and 8.10(1H, singlet).
i) Determine the double bond equivalence. ii) Draw the structure of the compound with proper
assignments. iii) Calculate the frequency shift (in Hz) of the proton with δ 8.10 ppm from TMS, in the
above NMR spectrometer.
B) What is the frequency shift of the resonance from TMS of a group of protons with δ = 6.33 in a
polypeptide in a spectrometer operating at 500 MHz?

Ans: A) i) DBE = 1 ii) iii) 2430 Hz, B) 3165 Hz.