Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

2 CONSISTENCY WITH EQNS. OF TYPE -d[A]/dt = k[A]"[BIb 379and(b) for the whole set, liIn calculating these averages, each value of the rate coefficient should be weightedby the reciprocal of the square of its standard error; if we write w(kuf) for theweight assigned to kof , we have.In practice, we do not know the value of a2 (kuf) and so we use the estimates2(kof) calculated from eqns. (63) and (70); i.e.The average of the rate coefficients of the uth group is given byand, since there are u groups in all,we obtain u values, El , li2 , . . . li,,average of the rate coefficients of the whole set is clearly. . . kU. TheNow, without going deeply into the underlying arguments, we can see that weshould be able to relate the scatter of the group means about the set mean to thedistribution of the individual rate coefficients within groups, if all groups are partof the same population. If there is no significant difference between groups, itcan be shown thatando=u 1=r,c c W(kof)(k - El2o=l f=1u-1r-uReferences p. 407