The Chlorine Rule: An Analysis of

Isotope Patterns of Compounds

Containing Multiple Bromine and
Chlorine Atoms
With an Introduction to the Isotope-Pattern Analyzer

Ray A. Gross, Jr.

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My Reasons for this Presentation

• Present results obtained at

PGCC
• Show that content found in
textbooks can be improved
• Motivate students

2
 Isotopes of Br and Cl

a b Ratio Rounde Variable

High (a/b) d # atoms
Low
ratio
mass mass

Br 79 81 (49.31) 1.028 1:1 m

(50.69)

Cl 35 (75.78) 37 3.129 3:1 n

(24.22)
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Mass Spectrometer

4
 100 61 59

77 Br
79
Bromobenzene

77
Br
81

M = 156 158 = M + 2

5
Schematic diagram of a mass spectrometer
 100 61 59

77 Br
79
Bromobenzene

77
Br
81

M = 156 158 = M + 2

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 52
100 32

77 Cl
Chlorobenzene
35

77
Cl
3:1
35

112 114

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 Why Br and Cl?

Br1Cl1 Br2Cl1 Br3Cl1

M +2 +4 M +2 +4 +6 M +2 +4 +6 +8

Molecular-ion peaks of C10H20Br1Cl1, C10H19Br2Cl1 and

C10H18Br3Cl1.
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 Premise

In lieu of pattern matching, it should be

possible to determine the number of Br
and Cl atoms in a molecular formula of a
compound by analyzing the molecular-
ion cluster (i.e., by cluster analysis).

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 Herbert C. Brown
Nobel Laureate

Hydroboration-oxidation
with BH3 (CHM 201)
Reduction with NaBH4
(CHM 202/204)

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 Lillian Berg
NVCC-Annandale 11
 100 61 59

77 100 98
Br
79 or 81 m = 1, n = 0
A=m+n=1
1:1
ArBrmCln T=A+1=2

M = 156 158 = M + 2

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 51:100:49
Br
m=2
n=0
Br A=2 1:2:1
T=3
ArBrmCln

234 238

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 34:100:97:32
Br

m=3
Br Br n=0
ArBrmCln A=3
1:3:3:1
T=4

312 318

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 18:68:100:66:16
Br
Br
m=4 1:4:6:4:1
Br n=0
Br A=4
ArBrmCln T=5

390 398

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 52
100 32
m=0
n=1
Cl
A=1
T=2

ArBrmCln 3:1

112 114

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 100:66:11
Cl
m=0
n=2 9:6:1
Cl A=2
T=3
ArBrmCln

146 150

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 27:27:9:1
Cl m=0
n=3
Cl Cl A=3
T=4
ArBrmCln

180 186

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 81:108:54:12:1

Cl
Cl m=0
n=4
Cl A=4
Cl
T=5
ArBrmCln

214 222

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 Chlorine Constant
3 1 3 4 1 3 7 5 1 3 10 12 6 1
3 1 3 4 1 3 7 5 1 3 11 13 6 1

Br0Cl1 Br1Cl1 Br2Cl1 Br3Cl1

M +2 M +2 +4 M +2 +4 +6 M +2 +4 +6 +8

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 Bromine Constant
1 1 3 4 1 9 15 7 1 27 54 36 10 1
1 1 3 4 1 10 16 7 1 30 59 38 10 1

Br1Cl0 Br1Cl1 Br1Cl2 Br1Cl3

M +2 M +2 +4 M +2 +4 +6 M +2 +4 +6 +8

IM = 3n
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 78 100 24
T=3
190 A=2
114 = Br + Cl
76 = benzene ring *L /R = 78/24 = 3
190 194

a disubstituted benzene n=1

m=1
ArBr1Cl1

190 194

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 T=4
A=3
*L /R = 63/7 = 9
224 230

Br = 79 n=2
L 2Cl = 70 L
149 m=1
Ar = 75
224 ArBr1Cl2
a bromodichlorobenzene

R R
224 230

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 Theoretical Considerations

Ideal Compounds
Br (a:b) = 1:1
Cl (a:b) = 3:1
13C and 2H negligible

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 Bromine Binomial
• Ratio (a:b) = 1:1

• (1a + 1b)m for Brm

• (1a + 1b)1 = 1a + 1b = 1:1

• (1a + 1b)2 = 1a2 + 2ab + 1b2 = 1:2:1

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 Chlorine Binomial
• Ratio (a:b) = 3:1

• (3a + 1b)n for Cln

• (3a + 1b)1 = 3a + 1b = 3:1

• (3a + b)2 = 9a2 + 6ab + 1b2 = 9:6:1

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 Ideal Model = Binomial Pair

(1a + m
1b) (3a + 1b) n

Br1Cl1

3a 2 + 4ab + 1b2 = 3:4:1

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 Results
(1a + 1b)m(3a + 1b)n = 1m3na(m + n) + …. +
1m1nb(m + n)
I(L/R) = 1m3n/1m1n
IM = 3n
Chlorine Rule: When I equals 1, 3, 9,
27 or 81; n is 0, 1, 2, 3, or 4,
respectively, where n = number of
chlorine atoms.
The number of bromine atoms m
equals A – n.
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J.Chem.Educ. 2004, 81, 1161-1168 (article available at front desk)
Roald Hoffmann-Nobel Laureate
Conservation of orbital symmetry

“Oxygen” Priestley vs Sheele

Hoffmann
Djerassi Woodward 29
Gross giving lecture with Hoffmann, Djerassi and
Woodward looking on. 30
 Structure Begets Properties
• Let’s examine structures.
• Assume 3:1 and 1:1 isotopic abundances
of chlorine and bromine.
• Consider Brm, Cln and BrmCln
compounds.

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 Br Br Br
* *
=

m = 1, N = 2 1 1
(156) (158)

Br Br Br Br Br
Br * Br * Br * Br * Br
=

m = 2, N = 4 1 2 1
(234) (236) (238)

Br Br Br Br
* Br * Br * Br * Br

Br
Br Br Br Br
Br
=
Br

m = 3, N = 8 Br Br Br Br
* Br * Br * Br * Br

Br Br Br Br
1 3 3 1
(312) (314) (316) (318) 32
 Cl Cl Cl Cl Cl
* * * *
=

n = 1, N = 4 3 1
(112) (114)

Cl Cl Cl Cl
* Cl * Cl * Cl * Cl

Cl Cl Cl Cl
* Cl * Cl * Cl * Cl
Cl
Cl
=
Cl Cl Cl Cl
n = 2, N = 16 * Cl * Cl * Cl * Cl

Cl Cl Cl Cl
* Cl * Cl * Cl * Cl

9 6 1
(146) (148) (150) 33
m = 1, n = 0 Br Br
N=2
1:1

m = 1, n = 1 BrCl BrCl BrCl BrCl

N=8 BrCl BrCl BrCl BrCl
3:4:1

m = 2, n = 1 BrClBr BrClBr BrClBr BrClBr

N = 16 BrClBr BrClBr BrClBr BrClBr
BrClBr BrClBr BrClBr BrClBr
BrClBr BrClBr BrClBr BrClBr
3:7:5:1

m = 2, n = 2 BrClBrCl BrClBrCl BrClBrCl BrClBrCl

BrClBrCl BrClBrCl BrClBrCl BrClBrCl
N = 64
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrC l
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrC l
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
BrClBrCl BrClBrCl BrClBrCl BrClBrCl
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9:24:22:8:1
 Results

N = 2m4n
N = 2m2n2n

N = 2A2n

Chem. Educ. 2003, 8, 182-186

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 Summary Part I
for BrmCln Compounds
• Derived a chlorine-rule equation, IM = 3n
• Applied it to find gross structures of
unknowns
• Derived a unit-sample equation, N = 2A2n

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Follow-on to the Chlorine Rule
• An automated A + 2 isotope-pattern
analyzer (IPA)
• IPA is on my website

J. Chem. Educ., in press

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 Example of a Print Out of a Mass
Spectrum in the Molecular-Ion Region
Mass Percent
224 64.4
225 4.3
226 100.0
227 6.9
228 45.6
229 3.2
230 6.4 38
Molecular-Ion Data is Entered
into the IPA

The Excel program returns the A

+ 2 (Cl, Br, S) composition of the
molecular formula

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 Homework Assignment
for
Selected Students
• Pick up slip from front desk
• Enter data from your slip into IPA
• Obtain the Cl, Br, S composition (e.g.,
Br1Cl2) and record it on your slip
• Write your name on the slip and turn it in
next Tuesday.

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Acknowledgement: Mass
Spectra from the Spectral
Data Base System (SDBS)

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Ende

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Lecture attended by hordes of
students eager to learn.

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Gross and Friends

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