ANSWER SCHEME

MASS SPECTROMETRY

1. An unknown substance shows a molecular ion peak at m/z = 170 with a relative
intensity of 100. The M + 1 peak has an intensity of 13.2, and the M + 2 peak has
an intensity of 1.00. What is the molecular formula of the unknown?
M at m/z = 170 (even number), might have 0 or even no. of Nitrogen >>> (nitrogen rule)
M peak it is the base peak because relative intensity is 100, no recalculation necessary
M + 1 peak = 13.2 / 1.1 = 12; 12 carbons
M + 2 peak = 1.00%, < 4% of M, so no S, Cl, Br

Mass (M) - mass (C, S, Cl, Br, F, and I) = mass (N, O, and H)
170 – (12)(12) = 26, C12H26 is possible (if has 0 Nitrogen)

Cannot have 2N, not enough molar mass for 2N left.

M + 2 peak, might indicate the presence of oxygen, O
170 – (12)(12) – 16 = 10, C12H10O (possible)

**answer: C12H10O (or C12H26)

2. An unknown hydrocarbon has a molecular ion peak at m/z = 84, with a relative
intensity of 31.3. The M + 1 peak has a relative intensity of 2.06, and the M + 2
peak has a relative intensity of 0.08. What is the molecular formula for this
substance?
M at m/z = 84 (even number), might have 0 or even no. of Nitrogen >>> (nitrogen rule)
M peak it is not the base peak because relative intensity is 31.3, need to recalculation
M = 31.3 = 31.3/31.3 x 100% = 100%
M + 1 = 2.06 = 2.06/31.3 x 100% = 6.58%, 6.58 / 1.1 = 5.98; 6 carbons
M + 2 = 0.08 = 0.08/31.3 x 100% = 0.25%, < 4% of M, so no S, Cl, Br

Mass (M) - mass (C, S, Cl, Br, F, and I) = mass (N, O, and H)
84 – (6)(12) = 12

**answer: C6H12 (no N and O because the molar mass left not enough for molar mass
oxygen or nitrogen)
 3. An unknown substance has a molecular ion peak at m/z = 107, with a relative
intensity of 100. The relative intensity of the M + 1 peak is 8.00, and the relative
intensity of the M + 2 peak is 0.30. What is the molecular formula for this unknown?
M at m/z = 107 (odd number), might have odd no. of Nitrogen (1,3,5..) >> (nitrogen rule)
M peak it is the base peak because relative intensity is 100, no recalculation necessary
M + 1 peak 8.00 / 1.1 = 7.3; 7 carbons
M + 2 peak 0.30%; < 4% no S, Cl, Br

Mass (M) - mass (C, S, Cl, Br, F, and I) = mass (N, O, and H)
107 – (1)(14) – (7)(12) = 9 (possible to have 1N only)

**answer: C7H9N

4. The mass spectral data of an unknown liquid are given below. What is the
molecular formula of this unknown?
m/z Intensity
78 23.6 (M+)
79 0.79
80 7.55
81 0.25
M at m/z = 78 (even number), might have 0 or even no. of Nitrogen >>> (nitrogen rule)
M peak it is not the base peak because relative intensity is 23.6%, need to recalculate
M = 23.6 = 23.6/23.6 x 100% = 100%
M + 1 = 0.79 = 0.79/23.6 x 100% = 3.35%, 3.35 / 1.1 = 3.05; 3 carbons
M + 2 = 7.55 = 7.55/23.6 x 100%, 32%, Cl is present because has ratio 3:1

Mass (M) - mass (C, S, Cl, Br, F, and I) = mass (N, O, and H)
78 – (3)(12) – 35 = 7 (nitrogen is 0, not enough molar mass left to have 2N)

**answer: C3H7Cl
 5. An organic compound composed of carbon, hydrogen and nitrogen. The carbon
atom constitutes more than 60% of the total mass with molecular ion at m/z is 112
amu observed in mass spectrum. Suggest the molecular formula of that
compound.
Compound X – C, H, N

M at m/z = 112 (even number), might have 0 or even no. of Nitrogen >>> (nitrogen rul
C = 60% of 112 amu

C = 60/100 x 112 amu = 67.2

= 67.2/12 = 5.6 (possible 6C)

Mass (M) - mass (C, S, Cl, Br, F, and I) = mass (N, O, and H)
N = 112 – 72 = 40

= 40/14 = 2.86 (possible to have 2N)

H = 112 – 72 – 28

= 12

**Answer is C6H12N2