143

Chapter 6

SENSITIVITY AND LIMIT OF DETECTION

6 . 1 . INTRODUCTION

There i s no d o u b t t h a t t h e detection l i m i t i s one of the most important

performance c h a r a c t e r i s t i c s of an analytical procedure. Progress i n a n a l y t i c a l
chemistry might well be measured by the s h i f t o f the detection l i m i t towards
lower values. Of course, t h e picture emerging would r e f l e c t only p a r t of the
progress. However, i t cannot be denied t h a t many problems in analytical
chemistry are problems of detecting and determining elements o r compounds i n
small amounts of sample (micro-analysis), of determining very low concentrations
or small amounts in l a r g e r samples ( t r a c e analysis) or even of determining low
concentrations in small samples.
Comparing analytical procedures by t h e i r l i m i t s of detection i s n o t easy.
I n many papers describing a n a l y t i c a l procedures no detection l i m i t s a r e given,
and t o the analyst facing the problem of choosing a procedure from several
a l t e r n a t i v e s , t h i s omission i s very disappointing. Even more disappointing i s
the lack of uniformity i n describing performances with respect t o the smallest
amounts o r concentrations t h a t can be detected o r determined.
Often a procedure i s s a i d t o be very s e n s i t i v e when the l i m i t of detection
i s low, and t h e l i m i t of detection and s e n s i t i v i t y in many instances a r e regarded
as synonymous. However, in o t h e r branches o f science s e n s i t i v i t y i s defined
as the slope of the curve t h a t i s obtained when the r e s u l t of the measurement
i s plotted against the amount t h a t i s t o be determined. I n analytical chemistry,
s e n s i t i v i t y defined i n t h i s way i s equal t o the slope of the analytical c a l i b r a t i o n
curve (Kaiser, 1965) and throughout t h i s book t h i s d e f i n i t i o n o f s e n s i t i v i t y
will be used. The lower l i m i t o f detection l i t e r a l l y i s t o be understood as
the l i m i t below which detection i s impossible. Although t h i s c l a r i f i e s the
144

meaning o f t h e term, i t c e r t a i n l y i s n o t s u f f i c i e n t when t h e d e t e c t i o n l i m i t i s

t o be used as a performance c h a r a c t e r i s t i c o f an a n a l y t i c a l procedure. It

appears t h a t q u a n t i f i c a t i o n o f t h i s c h a r a c t e r i s t i c g i v e s r i s e t o c o n s i d e r a b l e

c o n f u s i o n , as has been c l e a r l y demonstrated by C u r r i e (1968). F i g . 6.1, from

t h e paper o f C u r r i e , g i v e s s e v e r a l values o f l i m i t s o f d e t e c t i o n f o r a s p e c i f i c

r a d i o a c t i v i t y measurement process. These values were c a l c u l a t e d by u s i n g

different definitions. These d i f f e r e n c e s can be p a r t l y a s c r i b e d t o d i f f e r e n c e s

i n f o r m u l a t i n g t h e problem (when i s a component d e t e c t e d and w i t h what c e r t a i n t y ? ) .

5000
Definitions :
0

2000 - 1-background s t a n d a r d
d e v i a t i o n (oB)
1000
0 2-1D% o f t h e background
-5 500: 0 3-2oB
4-30g

E
200- 0 5-3Ugt3o~(oD=sample s t a n d a r d
deviation)
1007 6 - t w i c e t h e background
c 7-1000 dpm
.-
o 50: 0 8- 100 dps

: 20-
4-

0
4-

4
0
10- 0
5-1? I , I I I 1 t

1 2 3 4 5 6 7 8
definition
F i g . 6.1. "Ordered" d e t e c t i o n l i m i t s ; l i t e r a t u r e d e f i n i t i o n s . The d e t e c t i o n
l i m i t f o r a s p e c i f i c r a d i o a c t i v i t y measurement process i s p l o t t e d i n i n c r e a s i n g
o r d e r , a c c o r d i n g t o commonly-used a1 t e r n a t i v e d e f i n i t i o n s ( f r o m C u r r i e , 1968).
R e p r i n t e d w i t h p e r m i s s i o n ; c o p y r i g h t American Chemical S o c i e t y

Lower l i m i t s t o t h e d e t e c t i o n o f elements and compounds a r e s e t because o f

t h e presence o f e r r o r s ( n o i s e ) . T h e r e f o r e , a d e f i n i t i o n and q u a n t i f i c a t i o n o f

d e t e c t i o n l i m i t s must be based upon s t a t i s t i c s K a i s e r , 1947). I n t h i s chapter

on t h e d i s c u s s i o n o f t h e d e t e c t i o n l i m i t and r e a t e d q u a n t i t i e s , we s h a l l p a r t l y

f o l l o w C u r r i e (1968), who i n t r o d u c e d a d e c i s i o n l i m i t , a d e t e c t i o n l i m i t and

a determination l i m i t .
 145

6.2. SENSITIVITY AND THE ANALYTICAL CALIBRATION FUNCTION

The s e n s i t i v i t y o f a procedure designed f o r a q u a n t i t a t i v e a n a l y s i s can be

d e f i n e d as t h e s l o p e o f t h e a n a l y t i c a l c a l i b r a t i o n f u n c t i o n y = f ( x ) . This

c a l i b r a t i o n f u n c t i o n r e l a t e s t h e r e s u l t ( y ) o f t h e measuring process ( o u t p u t ,

a n a l y t i c a l s i g n a l ) t o t h e c o n c e n t r a t i o n o r amount ( x ) o f t h e component t o be

determined. The o u t p u t can be a meter r e a d i n g , an e l e c t r i c c u r r e n t o r v o l t a g e ,

a weight, etc. The s e n s i t i v i t y ( S ) can be w r i t t e n as t h e d i f f e r e n t i a l q u o t i e n t

F o r l i n e a r r e l a t i o n s h i p s between x and y and i n t h e absence o f a b l a n k , t h e

s e n s i t i v i t y i s s i m p l y t h e r a t i o between y and x. F i g . 6.2, from a paper o f

Specker (1968) c l e a r l y i l l u s t r a t e s t h e concept o f s e n s i t i v i t y ,

A
1.5

P
1 .o

0.5

0 i 2 3 4 5 6 7 8 9 10 F e ( p g / m l )
*
F i g . 6.2. C a l i b r a t i o n l i n e s f o r t h e photometric determination o f i r o n ( d e f i n i t i o n
o f s e n s i t i v i t y ) . L i n e 1, w i t h 2 - p y r i d i n e a l d o x i m e , AA/Ac = 0.18 ; l i n e 2, w i t h
o - y h e n a n t h r o l i n e , AE/Ac = 0.14 ; l i n e 3, w i t h 2,6-pyridinedicarboxylic a c i d ,
AA/Ac = 0.028. Thickness o f c e l l , 1 cm. O r d i n a t e , absorbance ; abscissa, i r o n
c o n c e n t r a t i o n . (From Specker, 1968).

These c a l i b r a t i o n graphs were o b t a i n e d by p l o t t i n g t h e absorbance a g a i n s t t h e

i r o n concentration. I t appears t h a t t h e d e t e r m i n a t i o n o f i r o n w i t h 2 - p y r i d i n e

aldoxime has a g r e a t e r s e n s i t i v i t y t h a n t h e procedures w i t h o-phenanthrol i n e

and w i t h 2,6-pyridinedicarboxylic a c i d .
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F o r purposes o f c h a r a c t e r i z i n g a n a l y t i c a l procedures, t h e s e n s i t i v i t y i s o f

l i m i t e d importance. F o r i n s t a n c e , t h e s e n s i t i v i t y can e a s i l y be i n f l u e n c e d

w i t h o u t a l t e r i n g t h e procedure s i g n i f i c a n t l y . Connecting an a m p l i f i e r t o t h e

o u t p u t o f an i n s t r u m e n t can e a s i l y b r i n g t h e o u t p u t from t h e m i l l i v o l t s t o t h e

v o l t s range and, a c c o r d i n g t o t h e d e f i n i ti on, t h e s e n s i t i v i t y i s t h e n increased

by a f a c t o r o f 1000. S i m i l a r l y , the s e n s i t i v i t y o f a photometric determination

can be i n c r e a s e d by i n c r e a s i n g t h e o p t i c a l p a t h l e n g t h .

However, e r r o r s ( n o i s e ) a r e u s u a l l y m a g n i f i e d t o t h e same e x t e n t .

S e n s i t i v i t i e s a r e seldom c o n s t a n t o v e r l a r g e c o n c e n t r a t i o n ranges and

s e n s i t i v i t i e s a r e t h e r e f o r e meaningful o n l y when c o n c e n t r a t i o n s o r c o n c e n t r a t i o n

ranges a r e s p e c i f i e d . Here again, s e n s i t i v i t i e s can be e a s i l y m a n i p u l a t e d ;

a wide v a r i e t y o f l i n e a r i z i n g d e v i c e s a r e a v a i l a b l e . T h i s does n o t mean, o f

course, t h a t any c a l i b r a t i o n graph i s a c c e p t a b l e t o t h e a n a l y t i c a l chemist, and

one must a t l e a s t be c a u t i o u s a b o u t n o n - l i n e a r c a l i b r a t i o n graphs. I n some

i n s t a n c e s , t h e o r e t i c a l c o n s i d e r a t i o n s can l e a d t o l i n e a r i z a t i o n o f C a l i b r a t i o n

graphs t h a t a r e f u l l y j u s t i f i e d , and t h e use o f l o g a r i t h m s i n spectrophotometry

(Boer-Lambert l a w s ) and p o t e n t i o m e t r y ( N e r n s t ) i s w e l l known i n t h i s r e s p e c t .

I n o t h e r i n s t a n c e s , n o n - l i n e a r graphs a r e due t o s a t u r a t i o n e f f e c t s , sometimes

even r e s u l t i n g i n a change o f s l o p e f r o m p o s i t i v e t o n e g a t i v e .

The range o v e r which t h e s e n s i t i v i t y can be c o n s i d e r e d t o be c o n s t a n t has,

o f course, a l o w e r and an upper l i m i t . By d e f i n i t i o n , t h e l o w e r l i m i t w i l l be

t h e d e t e c t i o n l i m i t (as d e f i n e d i n s e c t i o n 6.3) and t h e c o n c e n t r a t i o n where t h e

s e n s i t i v i t y begins t o change ( g o i n g f r o m l o w e r t o h i g h e r c o n c e n t r a t i o n s ) can be

regarded as t h e upper l i m i t . I n g e n e r a l , such a change w i l l be g r a d u a l and t h e

upoer l i m i t cannot be s p e c i f i e d u n l e s s a s p e c i f i c a t i o n i s g i v e n o f what i s t o

be c o n s i d e r e d t o be a s t r a i g h t c a l i b r a t i o n graph. A d e f i n i t i o n o f t h e upper

l i m i t m i g h t be t h e c o n c e n t r a t i o n where t h e response d i f f e r s by a c e r t a i n

percentage ( f o r i n s t a n c e , 3%) f r o m t h e response t h a t m i g h t be expected f r o m t h e

s e , i s i t i v i t y near t h e d e t e c t i o n l i m i t . As f a r as we know, no g e n e r a l l y accepted

d e f i n i t i o n o f t h e upper l i m i t and t h u s o f t h e l i n e a r (dynamic) range f o r

 147

characterizing a procedure has been proposed. The concept of the l i n e a r range

i s i l l u s t r a t e d in Fig. 6.3. The l i n e a r range i s usually expressed as the number
of decades between the lower and upper l i m i t .

input, x
Fig. 6.3.

As has been s t a t e d , the s e n s i t i v i t y as a means of characterizing procedures

i s of limited value, and t h i s i s p a r t i c u l a r l y t r u e f o r c a l i b r a t i o n graphs near

the (lower) l i m i t of detection. However, f o r a good understanding of the
general nature of analytical procedures, the s e n s i t i v i t y i s a useful parameter
( s e e Part V ) , and i t i s a l s o a useful parameter when discussing the s e l e c t i v i t y
and speci f i c i t y of analytical procedures (Chapter 7 ) .

6.3. D E C I S I O N LIMIT

When the a n a l y t i c a l chemist accepts t h a t random e r r o r s a r e unavoidable, he

a l s o has t o accept t h a t there a r e l i m i t s t o the detection (and thus t o the
determination) of elements and compounds. He i n t u i t i v e l y may feel t h a t i t makes
no sense t o d e t e c t or determine amounts t h a t are smaller than the random e r r o r s

inherent t o the procedure used. In f a c t , a rough estimate of the detection

l i m i t could be made by taking the value o f the standard deviation ( i n u n i t s of
concentration o r amount). However, t h i s rough p i c t u r e needs some refinement.
148

The c o n c e n t r a t i o n o r amount o f t h e component t o be determined ( x ) can be

c a l c u l a t e d from t h e measurement ( y ) by making use o f t h e c a l i b r a t i o n f u n c t i o n

( y = f ( x ) ). The d i s c u s s i o n w i l l be g i v e n i n terms o f s i g n a l s . Usually y i s

regarded as t h e d i f f e r e n c e between two measurements, i.e., a measurement o f t h e

unknown sample (y,) and a measurement o f t h e b l a n k (ybl). Then t h e problem can

be f o r m u l a t e d i n two ways which a r e e s s e n t i a l l y t h e same : i t can be q u e s t i o n e d

whether yu- ybl d i f f e r s s i g n i f i c a n t l y f r o m zero o r whether yu d i f f e r s

s i g n i f i c a n t l y f r o m yb,. O f course, t h i s problem can be a t t a c k e d o n l y by means

o f statistics. However, t o make any statements a t a l l some assumptions have

t o be made a b o u t t h e d i s t r i b u t i o n o f e r r o r s . The case o f a normal d i s t r i b u t i o n

o f t h e r e a d i n g o f t h e b l a n k i s r e p r e s e n t e d i n F i g . 6.4. The s t a n d a r d d e v i a t i o n

i s denoted by ubl and t h e t r u e v a l u e o r l i m i t i n g mean o f t h e b l a n k by ybl.

F i g . 6.4. Normal d i s t r i b u t i o n

I t i s c l e a r t h a t t h e probab l i t y o f measuring s i g n a l s ybl > L w i l l be

C

where p(ybl) r e p r e s e n t s t h e d i s t r i b u t i o n f u n c t i o n o f ybl. If s i g n a l s l a r g e r

t h a n t h e d e c i s i o n l i m i t , Lc, a r e i n t e r p r e t e d as "component p r e s e n t " , a f r a c t i o n

(x o f t h e measurements o f t h e b l a n k i s m i s i n t e r p r e t e d .
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The d e c i s i o n l i m i t can be expressed i n terms o f s i g n a l s by

Conversion i n t o c o n c e n t r a t i o n s i s e a s i l y p o s s i b l e by m u l t i p l i c a t i o n w i t h t h e

c a l i b r a t i o n constant.

I n t r o d u c i n g a v a l u e o f kc = 3 l e a d s t o 1-a = 99.86%. Then L c i s equal t o

K a i s e r ' s d e t e c t i o n l i m i t ( K a i s e r , 1947). The c h o i c e o f kc, o f course, i s a r b i t r a r y

and depends on t h e c o n f i d e n c e t h a t i s r e q u i r e d f o r t h e answer t o t h e q u e s t i o n

o f whether t h e component i s d e t e c t e d o r n o t . The d e c i s i o n l i m i t , Lc, cannot,

i n p r i n c i p l e , be used as a q u a l i t y c r i t e r i o n f o r t h e a n a l y t i c a l procedure ( C u r r i e ,

1968 ; Svoboda and Gerbatsch, 1968 ; Wilson, 1970). T h i s i s i l l u s t r a t e d by

F i g . 6.5, where t h e two p r o b a b i l i t y d i s t r i b u t i o n f u n c t i o n s o f ybl and yu o v e r l a p .

The d i s t r i b u t i o n o f yu i s chosen t o have a maximum a t yu = Lc. Thus, F i g . 6.5

r e p r e s e n t s a s i t u a t i o n o f a l a r g e number o f r e p e a t e d measurements on a sample

w i t h a concentration corresponding ( v i a the c a l i b r a t i o n constant) t o t h e

d e c i s i o n l i m i t , Lc.

F i g . 6.5. I l l u s t r a t i o n o f decision l i m i t ,

The s t a n d a r d d e v i a t i o n s crbl and uu a r e c o n s i d e r e d t o be equal (which i s

u s u a l l y t h e case f o r s m a l l c o n c e n t r a t i o n s ) . S i g n a l s l a r g e r t h a n Lc can be

i n t e r p r e t e d by "Component p r e s e n t " . However, a f r a c t i o n o f t h e measurements

150

on a sample with a content L c of the component t o be detected w i l l y i e l d s i g n a l s

smaller than L c . B i s given by

LC
B = J P(Y,) dyU (6.4)
-02

From Fig. 6 . 5 , i t appears t h a t B = 0.5 and the statement about t h e absence o f

the component i s very unreliable. To express this d i f f e r e n t l y : the e r r o r of
the f i r s t type (deciding t h a t the component i s present when i t i s n o t ) i s

small ( a ) , whereas the e r r o r of t h e second type (deciding t h a t the component

i s absent when i t i s present) i s l a r g e (B) (see a l s o 3.2.1 and Chapter 2 ) .

Signals l a r g e r than Lc can be i n t e r p r e t e d as the detection of the component with

quasi c e r t a i n t y , whereas s i g n a l s smaller than L allow no decision t o be made

C
about the absence of the component.

6.4. DETECTION LIMIT

The u p06Rehi0hi decision about t h e presence of a component from a measured

signal has resulted in a d e f i n i t i o n of the decision l i m i t as given above. In

order to characterize an analytical procedure, i t i s necessary t o define a

level LD specifying the detection c a p a b i l i t i e s of the a n a l y t i c a l procedure.

This l e v e l , the detection l i m i t , should correspond t o a concentration t h a t , with

g r e a t p r o b a b i l i t y , will y i e l d s i g n a l s t h a t can be distinguished from the s i g n a l s

obtained from t h e blank. This, of course, corresponds t o reducing the e r r o r o f

the second type, and thus of reducing a. I n F i g . 6.6 a s i t u a t i o n i s represented

where a = 6. Here the limiting mean of yu can be used f o r defining a detection

limit, LD

LD = ybl t kd obi = Lc + k ' u

d bl

Here again the standard deviations of t h e d i s t r i b u t i o n s p ( y b l ) and p(y,) have

been assumed t o be i d e n t i c a l . The detection l i m i t as defined by eqn. 6.5 i s

equal t o the l i m i t of guarantee of purity as defined by Kaiser (1965) when
 151

F i g . 6.6. I l l u s t r a t i o n o f detection l i m i t .

k d = 6 and k I d = 3. I f a c o n c e n t r a t i o n i s equal t o t h e d e t e c t i o n l i m i t , i t can

be d e t e c t e d w i t h 99.86% c e r t a i n t y . S m a l l e r c o n c e n t r a t i o n s cannot be d e t e c t e d

u n l e s s a s m a l l e r c o n f i d e n c e i s accepted.

6.5. DETERMINATION LIMIT

A d e t e r m i n a t i o n l i m i t can be d e f i n e d as t h e l i m i t a t which a g i v e n procedure

w i l l be s u f f i c i e n t l y p r e c i s e t o y i e l d a s a t i s f a c t o r y q u a n t i t a t i v e e s t i m a t e o f

t h e unknown c o n c e n t r a t i o n . Such a l i m i t , L can be d e f i n e d i n terms o f ybl

q'
and obi, a g a i n assuming t h a t t h e s t a n d a r d d e v i a t i o n s f o r b l a n k and unknown

ars identical. One can w r i t e t h a t t h e corresponding s i g n a l i s

and i t can e a s i l y be shown t h a t t h e r e l a t i v e s t a n d a r d d e v i a t i o n o b t a i n e d f r o m

measurements a t t h i s l e v e l i s l / k
9'
The r e l a t i v e s t a n d a r d a e v i a t i o n o f t h e " q u a n t i t a t i v e " measurement a t t h e
1 2
d e c i s i o n l e v e l Lc w i l l be 335%, and a t LD 163%.

6.6. DISCUSSION

No a t t e m p t w i l l be made t o discu'ss i n d e t a i l t h e s e v e r a l aspect; o f the

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d e c i s i o n l i m i t , t h e d e t e c t i o n l i m i t and t h e d e t e r m i n a t i o n l i m i t , and t h e

r e a d e r i s r e f e r r e d t o t h e l i t e r a t u r e a l r e a d y c i t e d and t o t h e c o n t r i b u t i o n s o f

K a i s e r (1966), E h r l i c h (1969), L i t e a n u and Rica (1973, 1975) and I n g l e (1974).

However, i t i s necessary t o make some remarks about t h e use o f t h e concepts

introduced i n t h i s chapter. D e f i n i t i o n s have been f o r m u l a t e d i n terms o f t h e

l i m i t i n g mean o f t h e b l a n k (ybl) and t h e s t a n d a r d d e v i a t i o n . I n practice, only

a l i m i t e d number o f experiments w i l l be a v a i l a b l e f o r t h e e s t i m a t i o n o f these

quantities. I f t h e e s t i m a t e s a r e used f o r c a l c u l a t i o n o f t h e l i m i t s o f d e c i s i o n

and d e t e c t i o n , an u n c e r t a i n t y i s i n t r o d u c e d , and d e c i d i n g whether a measurement

o f t h e unknown d i f f e r s s i g n i f i c a n t l y f r o m t h e b l a n k s h o u l d t h e r e f o r e be c a r r i e d

o u t w i t h t h e t - t e s t ( C u r r i e , 1968 ; G a b r i e l s , 1970 ; Plesch, 1975). T h i s means

t h a t t h e 'constants kc and k d i n eqns. 6.3 and 6.5 s h o u l d be r e p l a c e d by t - f a c t o r s

derived from Student's t - d i s t r i b u t i o n . S u r e l y t h e d e t e c t i o n l i m i t does n o t

change by o r d e r s o f magnitude i f a reasonable number o f measurements o f t h e

b l a n k have been made. As l o n g as t h e r e i s no consensus about d e f i n i t i o n s , t h e r e

s h o u l d n e v e r be d o u b t about t h e way i n which l i m i t s have been c a l c u l a t e d . In

a way we agree w i t h W i l s o n (1973), who doubts t h e u s e f u l n e s s o f t h e d e t e c t i o n

l i m i t as a performance c h a r a c t e r i s t i c . W i l s o n proposes t o s u p p l y i n f o r m a t i o n

on t h e s t a n d a r d d e v i a t i o n o f t h e b l a n k . The d e t e c t i o n l i m i t i s e a s i l y

c a l c u l a t e d from t h e s t a n d a r d d e v i a t i o n and i t s r e l i a b i l i t y can be t a k e n i n t o

account when t h e number o f degrees o f freedom i s known. I t s h o u l d be n o t e d

t h a t i n g e n e r a l i t i s n o t p e r m i s s i b l e t o c a l c u l a t e d e t e c t i o n l i m i t s from

s t a n d a r d d e v i a t i o n s o b t a i n e d f r o m measurements a t c o n c e n t r a t i o n l e v e l s much

h i g h e r t h a n t h e d e t e c t i o n l i m i t , o r a t l e a s t t h e a n a l y s t has t o be aware o f

the p i t f a l l s i n doing so. Standard d e v i a t i o n s a r e u s u a l l y a f u n c t i o n o f

concentration. C o m p l i c a t i o n s can a l s o a r i s e from n o n - l i n e a r i t y o f t h e c a l i b r a t i o n

function. F o r d e t a i l s , t h e r e a d e r i s r e f e r r e d t o t h e papers by I n g l e and

W i l s o n (1976) and L i teanu e t a l . (1976).

D e t e c t i o n l i m i t s s h o u l d be regarded as c h a r a c t e r i s t i c s o f w e l l d e s c r i b e d

a n a l y t i c a l procedures. I t makes no sense, f o r i n s t a n c e , t o s p e c i f y t h e d e t e c t i o n

 153

l i n i t f o r t i t r a t i o n s i n general. A change i n c o n d i t i o n s w i l l l e a d t o a change

i n t h e procedure and p o s s i b l y t o a change i n t h e l i m i t s .

The n a t u r e o f t h e procedure ( u s u a l l y t h e measurement) w i l l e i t h e r l e a d t o

a f o r m u l a t i o n o f t h e d e t e c t i o n l i m i t i n terms o f amounts o f t h e component t o

be d e t e c t e d o r i n terms o f c o n c e n t r a t i o n s . W i t h s p e c i f i e d amounts o f sample,

c o n c e n t r a t i o n s can e a s i l y be c o n v e r t e d i n t o amounts, and vice v e ~ a . O f course,

s i m i l a r r e a s o n i n g a p p l i e s t o t h e s e n s i t i v i t y and t h e l i n e a r range. However, i t

i s e s s e n t i a l t o s p e c i f y t h e u n i t s when q u o t i n g v a l u e s f o r t h e performance

c h a r a c t e r i s t i c s w i t h o u t c o n v e r t i n g , f o r i n s t a n c e , c o n c e n t r a t i o n s i n t o amounts.

Such a c o n v e r s i o n can e a s i l y obscure t h e m e r i t s o f t h e procedure.

6.7. GAS CHROMATOGRAPH1C DETECTORS

The d e s c r i p t i o n o f a number o f gas chromatographic d e t e c t o r s by Hartmann

(1971) w i l l s e r v e as an i l l u s t r a t i o n o f t h e (use of t h e ) concepts i n t r o d u c e d

i n t h i s chapter. The s e t o f c h a r a c t e r i s t i c s as g i v e n i n Table 6 . 1 ( t a k e n f r o m

t h e paper by Hartmann) c o n s i s t s o f t h e s e n s i t i v i t y , t h e n o i s e and t h e l i n e a r

range. I n a d d i t i o n , some o f t h e o p e r a t i n g c o n d i t i o n s have been s p e c i f i e d . The

r e a d e r s h o u l d be aware o f t h e f a c t t h a t f o r purposes o f s e l e c t i o n o f t h e " b e s t "

detector, the information gathered i n t h i s t a b l e i s incomplete. The f i g u r e s

apply t o a s e t o f s p e c i f i c o p e r a t i n g c o n d i t i o n s , a l t h o u g h i t can be assumed

t h a t t h e s e o p e r a t i n g c o n d i t i o n s have been o p t i m i z e d . I t s h o u l d a l s o be n o t e d

t h a t t h e f i g u r e s w i l l be d i f f e r e n t f o r d i f f e r e n t compounds.

The s e n s i t i v i t y used by Hartmann i s e s s e n t i a l l y t h e same c h a r a c t e r i s t i c as

d e f i n e d i n s e c t i o n 6.2. However, a d i r e c t measurement o f t h e s e n s i t i v i t y o f

a gas chromatographic d e t e c t o r would i n v o l v e a f e e d o f known c o n c e n t r a t i o n and

measurement o f t h e o u t p u t . The values i n t h e t a b l e a p p a r e n t l y a r e d e r i v e d

from peak areas, t h e f l o w v e l o c i t y o f t h e c a r r i e r gas and t h e w e i g h t o f t h e

sample i n j e c t e d . The f i g u r e s d e r i v e d i n t h i s way a r e average s e n s i t i v i t i e s ,

which, o f course, a r e i d e n t i c a l w i t h t h e s e n s i t i v i t i e s p r o v i d e d t h a t t h e y can

be c o n s i d e r e d t o be c o n s t a n t i n t h e c o n c e n t r a t i o n range covered by t h e
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 155

chromatographic peak. I t i s i m p o r t a n t t o n o t e t h a t t h e u n i t s used n the

e x p r e s s i o n f o r t h e s e n s i t i v i t i e s a r e dependent on t h e n a t u r e o f t h e d e t e c t o r .

F o r i n s t a n c e , t h e thermal c o n d u c t i v i t y d e t e c t o r responds t o changes i n

c o n c e n t r a t i o n whereas t h e f l a m e - i o n i z a t i o n d e t e c t o r responds t o t h e mass o f

t h o compound e n t e r i n g t h e d e t e c t o r p e r u n i t t i m e . F o r t h i s reason, amongst

o t h e r s ( s e e s e c t i o n 6 . 2 ) , i t i s d i f f i c u l t t o compare d e t e c t o r s by t h e i r

sensi ti v i t i e s .

The n o i s e quoted by Hartmann (1971) i s d e f i n e d as t h e average peak-to-peak

a m o l i t u d e measured a t t h e o u t p u t . Depending on t h e n a t u r e o f t h e n o i s e , t h e

average a m p l i t u d e , N , can be p u t equal t o t h e d e c i s i o n l i m i t , Lc, as d e f i n e d i n

t h i s c h a p t e r ( N r o u g h l y equals 40) and expressed i n u n i t s o f t h e o u t p u t ( y ) .

The d e t e c t a b i l i t y , 2N/S, t h e n r o u g h l y approximates t h e d e t e c t i o n l i m i t ,

LD’
expressed i n u n i t s o f t h e i n p u t ( x ) o f t h e d e t e c t o r . Again, these u n i t s a r e

d i f f e r e n t f o r t h e several detectors.

I n o r d e r t o compare these d e t e c t o r s i n c o m b i n a t i o n w i t h a chromatographic

column, t h e d e t e c t i o n l i m i t 3f t h e d e t e c t o r has t o be c o n v e r t e d i n t o t h e

d e t e c t i o n l i m i t o f a gas chromatographic procedure. T h i s can e a s i l y be done

when t h e c a r r i e r gas v e l o c i t y , t h e peak w i d t h and t h e amount o f sample a r e

known. Assuming t h a t t h e c h a r a c t e r i s t i c s would a p p l y when t h e c a r r i e r gas

v e l o c i t y i s 50 ml/min. i n a l l i n s t a n c e s and t h e peak w i d t h a t h a l f h e i g h t i s

1 2 sec. ( o r 10 m l ) , one can a r r i v e a t t h e d e t e c t i o n l i m i t s o f t h e procedure

q u o t e d i n T a b l e 6 . 1 by s i m p l y m u l t i p l y i n g t h e d e t e c t i o n l i m i t o f t h e d e t e c t o r

by t h e peak w i d t h . These d e t e c t i o n l i m i t s n e c e s s a r i l y a r e n o t e x a c t and can

serve o n l y as rough f i g u r e s f o r comparing d e t e c t o r s . A b e t t e r comparison

would be p o s s i b l e o n l y when more d e t a i l s o f t h e b e h a v i o u r o f t h e whole system,

i.e., detector + column + injector + compound t o be determined, a r e k n o w .

156

REFERENCES

L.A. Currie, Anal. Chem., 40 (1968) 586.

G. Ehrlich, Wissenschaftl. Zeitschr. , 11 (1969) 22.
R . Gabriels, Anal. Chem., 42 (1970) 1439.
C . H . Hartmann, Anal. Chem., 43(2) (1971) 113A.
J.D. Ingle, J . Chem. Educ., 51 (1974) 100.
J.D. Ingle and R.L. Wilson, Anal. Chem., 48 (1976) 1641.
H. Kaiser, Spectrochim; Acta, 3 (1947) 40.
H . Kaiser, Z. Anal. Chem., 209 (1965) 1.
H. Kaiser, Z . Anal. Chem., 216 (1966) 80.
C . Liteanu and I . Rica, Mikrochim. Acta, (1973) 745.
C . Liteanu and I . Rica, Mikrochim. Acta, (1975) 311.
C. Liteanu, E. Hopirtean and C. Popescu, Anal. Chem., 48 (1976) 2013.
R. Plesch, GIT (Glas-Instrum.-Tech.) Fachz. Lab. , 19 (1975) 676.
H . Specker, Angew. Chem., I n t . Ed. Engl., 7 (1968) 252.
V. Svoboda and R. Gerbatsch, Z . Anal. Chem., 242 (1968) 1.
A . L . Wilson, Talanta, 20 (1973) 725.