Mayo–Lewis equation

The Mayo–Lewis equation or copolymer equation in polymer chemistry describes the distribution of
monomers in a copolymer. It was proposed by Frank R. Mayo and Frederick M. Lewis.[1]

The equation considers a monomer mix of two components and and the four different reactions
that can take place at the reactive chain end terminating in either monomer ( and ) with their
reaction rate constants :

The reactivity ratio for each propagating chain end is defined as the ratio of the rate constant for addition
of a monomer of the species already at the chain end to the rate constant for addition of the other
monomer.[2]

The copolymer equation is then:[3][4][2]

with the concentrations of the components in square brackets. The equation gives the relative instantaneous
rates of incorporation of the two monomers.[4]

Equation derivation
Monomer 1 is consumed with reaction rate:[5]

with the concentration of all the active chains terminating in monomer 1, summed over chain

{\displays
lengths. is defined similarly for monomer 2.
Likewise the rate of disappearance for monomer 2 is:

Division of both equations by followed by division of the first equation by the second yields:

The ratio of active center concentrations can be found using the steady state approximation, meaning that
the concentration of each type of active center remains constant.

The rate of formation of active centers of monomer 1 ( ) is equal to the rate of their
destruction ( ) so that

or

Substituting into the ratio of monomer consumption rates yields the Mayo–Lewis equation after
rearrangement:[4]

Mole fraction form

It is often useful to alter the copolymer equation by expressing concentrations in terms of mole fractions.
Mole fractions of monomers and in the feed are defined as and where

Similarly, represents the mole fraction of each monomer in the copolymer:

These equations can be combined with the Mayo–Lewis equation to give[6][4]

This equation gives the composition of copolymer formed at each instant. However the feed and copolymer
compositions can change as polymerization proceeds.

Limiting cases
Reactivity ratios indicate preference for propagation. Large indicates a tendency for to add ,
while small corresponds to a tendency for to add . Values of describe the tendency of
to add or . From the definition of reactivity ratios, several special cases can be derived:

If both reactivity ratios are very high, the two monomers only react with
themselves and not with each other. This leads to a mixture of two homopolymers.
. If both ratios are larger than 1, homopolymerization of each monomer is
favored. However, in the event of crosspolymerization adding the other monomer, the chain-
end will continue to add the new monomer and form a block copolymer.
. If both ratios are near 1, a given monomer will add the two monomers with
comparable speeds and a statistical or random copolymer is formed.
If both values are near 0, the monomers are unable to homopolymerize. Each
can add only the other resulting in an alternating polymer. For example, the copolymerization
of maleic anhydride and styrene has reactivity ratios = 0.01 for maleic anhydride and =
[7]
0.02 for styrene. Maleic acid in fact does not homopolymerize in free radical
polymerization, but will form an almost exclusively alternating copolymer with styrene.[8]
In the initial stage of the copolymerization, monomer 1 is incorporated faster
and the copolymer is rich in monomer 1. When this monomer gets depleted, more monomer
2 segments are added. This is called composition drift.
When both , the system has an azeotrope, where feed and copolymer composition are
the same.[9]

Calculation of reactivity ratios

Calculation of reactivity ratios generally involves carrying out several polymerizations at varying monomer
ratios. The copolymer composition can be analysed with methods such as Proton nuclear magnetic
resonance, Carbon-13 nuclear magnetic resonance, or Fourier transform infrared spectroscopy. The
polymerizations are also carried out at low conversions, so monomer concentrations can be assumed to be
constant. With all the other parameters in the copolymer equation known, and can be found.

Curve Fitting

One of the simplest methods for finding reactivity ratios is plotting the copolymer equation and using
nonlinear least squares analysis to find the , pair that gives the best fit curve. This is preferred as
methods such as Kelen-Tüdős or Fineman-Ross (see below) that involve linearization of the Mayo–Lewis
equation will introduce bias to the results.[10]

Mayo-Lewis Method
The Mayo-Lewis method uses a form of the copolymer equation relating to :[1]

For each different monomer composition, a line is generated using arbitrary values. The intersection of
these lines is the , for the system. More frequently, the lines do not intersect in a single point and the
area in which most lines intersect can be given as a range of , and values.

Fineman-Ross Method

Fineman and Ross rearranged the copolymer equation into a linear form:[11]

where and

Thus, a plot of versus yields a straight line with slope and intercept

Kelen-Tüdős method

The Fineman-Ross method can be biased towards points at low or high monomer concentration, so Kelen
and Tüdős introduced an arbitrary constant,

where and are the highest and lowest values of from the Fineman-Ross method.[12] The
data can be plotted in a linear form

{\displaystyle

where and . Plotting against yields a straight line that gives

when and when . This distributes the data more symmetrically and can yield better
results.

Q-e scheme

A semi-empirical method for the prediction of reactivity ratios is called the Q-e scheme which was proposed
by Alfrey and Price in 1947.[13] This involves using two parameters for each monomer, and . The
reaction of radical with monomer is written as

{\displaystyle
while the reaction of radical with monomer is written as

Where P is a proportionality constant, Q is the measure of reactivity of monomer via resonance stabilization,
and e is the measure of polarity of monomer (molecule or radical) via the effect of functional groups on
vinyl groups. Using these definitions, and can be found by the ratio of the terms. An advantage of this
system is that reactivity ratios can be found using tabulated Q-e values of monomers regardless of what the
monomer pair is in the system.

External links
copolymers @zeus.plmsc.psu.edu Link (http://zeus.plmsc.psu.edu/~manias/MatSE443/chapt
er5.pdf)

References
1. Copolymerization. I. A Basis for Comparing the Behavior of Monomers in Copolymerization;
The Copolymerization of Styrene and Methyl Methacrylate Frank R. Mayo and Frederick M.
Lewis J. Am. Chem. Soc.; 1944; 66(9) pp 1594 - 1601; doi:10.1021/ja01237a052 (https://doi.
org/10.1021%2Fja01237a052)
2. Cowie, J.M.G. Polymers: Chemistry & Physics of Modern Materials (2nd ed., Chapman &
Hall 1991) p.106 ISBN 0-412-03121-3
3. Fried, Joel R. Polymer Science & Technology (2nd ed., Prentice-Hall 2003) p.42 ISBN 0-13-
018168-4
4. Rudin, Alfred The Elements of Polymer Science and Engineering (Academic Press 1982)
p.265 ISBN 0-12-601680-1
5. Young, Robert J. (1983). Introduction to polymers (https://archive.org/details/introductiontopo
00youn_0) ([Reprinted with additional material] ed.). London: Chapman and Hall. ISBN 0-
412-22170-5.
6. Fried, Joel R. Polymer Science & Technology (2nd ed., Prentice-Hall 2003) p.44 ISBN 0-13-
018168-4
7. Copolymer Reactivity Ratios. Polymer Handbook, 4th ed,; Wiley, 2003; Vol 1, pp 259.
8. Rudin, Alfred The Elements of Polymer Science and Engineering (Academic Press 1982)
p.288 ISBN 0-12-601680-1
9. Rudin, Alfred The Elements of Polymer Science and Engineering (Academic Press 1982)
p.270 ISBN 0-12-601680-1
10. Tidwell, Paul W.; Mortimer, George A. (1965). "An Improved Method of Calculating
Copolymerization Reactivity Ratios" (https://onlinelibrary.wiley.com/doi/10.1002/pol.1965.10
0030137). J. Polym. Sci. A. 3: 369–387. doi:10.1002/pol.1965.100030137 (https://doi.org/10.
1002%2Fpol.1965.100030137). Retrieved 14 September 2021.
11. Fineman, M.; Ross, S. D. J. Polymer Sci. 1950, 5, 259.
12. Kelen, T.; Tüdős, F.; Turcsányi, B. Polymer Bull. 1980, 2, 71-76.
13. Seymour, Raymond; Carraher, Charles Jr (1981). Polymer chemistry : an introduction. M.
Dekker. p. 326. ISBN 0-8247-6979-1.

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