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preface to fifteenth edition

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11.28 SECTION 11<br />

11.4.2.2 Partition Ratio. The partition ratio is the additional time a solute band takes <strong>to</strong> elute,<br />

as compared with an unretained solute (for which k 0), divided by the elution time of an unre-<br />

tained band:<br />

Retention time may be expressed as<br />

t t<br />

k <br />

t<br />

V V<br />

<br />

V<br />

R M R M<br />

M<br />

L<br />

tR<br />

t M(1 k) (1 k)<br />

u<br />

11.4.2.3 Relative Retention. The relative retention of two solutes, where solute 1 elutes before<br />

solute 2, is given variously by<br />

M<br />

k 2 V R,2 t R,2<br />

<br />

k V t<br />

1 R,1 R,1<br />

The relative retention is dependent on (1) the nature of the stationary and mobile phases and (2) the<br />

column operating temperature.<br />

11.4.2.4 Column Efficiency. Under ideal conditions the profile of a solute band resembles that<br />

given by a Gaussian distribution curve (Fig. 11.1). The efficiency of a chroma<strong>to</strong>graphic system is<br />

expressed by the effective plate number N eff , defined from the chroma<strong>to</strong>gram of a single band,<br />

<br />

L t R<br />

t<br />

Neff 16 5.54<br />

H W W<br />

2 2<br />

R<br />

b 1/2<br />

where L is the column length, H is the plate height, t R is the adjusted time for elution of the band<br />

center, W b is the width at the base of the peak (Wb<br />

4) as determined from the intersections of<br />

tangents <strong>to</strong> the inflection points with the baseline, and W 1/2 is the width at half the peak height.<br />

Column efficiency, when expressed as the number of theoretical plates N theor uses the uncorrected<br />

retention time in the foregoing expression. The two column efficiencies are related by<br />

N<br />

k<br />

2<br />

eff Ntheor <br />

k 1<br />

11.4.2.5 Band Asymmetry. The peak asymmetry fac<strong>to</strong>r AF is often defined as the ratio of peak<br />

half-widths at 10% of peak height, that is, the ratio b/a, as shown in Fig. 11.2. When the asymmetry<br />

ratio lies outside the range 0.95–1.15 for a peak of k 2, the effective plate number should be<br />

calculated from the expression<br />

41.7(t/W ) R 0.1<br />

N (a/b) 1.25<br />

11.4.2.6 Resolution. The degree of separation or resolution, Rs, of two adjacent peaks is defined<br />

as the distance between band peaks (or centers) divided by the average bandwidth using W b ,as<br />

shown in Fig. 11.3.<br />

tR,2 tR,1<br />

Rs 0.5(W 2 W 1 )

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