Harris QCA 8e Chapter 18

1 of 14
At 510 nm, the molar absorptivities for two complexes (A and ! are "#,400 and 5$50 %
&
1
cm
&1
, respectivel'( )he absorbance in a 1(00 mm c*vet of a sol*tion with +A, - 1(00 x 10
&4

% and +, - $(00 x 10
&4
% wo*ld be
(a! 0(4#.(
(b! 4(#.(
(c! 0(/80(
$ of 14
A sol*tion containin0 two complexes (1 and 2! was anal'3ed with a 4pectronic $0
instr*ment *sin0 1(00 cm cells( 5xperimentall', it was determined that complex 1 has a
molar absorptivit' of 5$,800 %
&1
cm
&1
at 4#0 nm, while complex 2 has a molar absorptivit' of
$,1#0 %
&1
cm
&1
at this wavelen0th( )he absorbance of the sol*tion at 4#0 nm was recorded as
0(4#$( A second readin0 was ta6en at #80 nm where the molar absorptivit' of complex 1
was reported to be 1#,800 %
&1
cm
&1
, and the molar absorptivit' of complex 2 is 1,08$ %
&1
cm
&
1
( )he absorbance of the sol*tion at #80 nm was fo*nd to be 0(185( Calc*late the
concentration of complex 1 in the sol*tion(
(a! 8(/5 x 10
&#
%olar
(b! .(/" x 10
&5
%olar
(c! 4(// x 10
&#
%olar
" of 14
)he presence of an isobestic point indicates
(a! that there are at least two different compo*nds present in the sol*tion bein0 eval*ated(
(b! that one absorbin0 species is bein0 converted to another absorbin0 species d*rin0 a
chemical reaction(
(c! that three or more absorbin0 species have an intersectin0 absorbance at a specific
wavelen0th(
4 of 14
Chemists often will *se a 4catchard plot to determine the e7*ilibri*m constant for a
chemical reaction( 8n the reaction 9 : 1 91, which of the followin0 best ill*strates a
4catchard 9lot;
(a! A 0raph of <A=+1, vers*s <A will be a strai0ht line with a slope of &K when <A - (the
observed absorbance! (the initial absorbance! for each point in the titration of 9 with 1(
(b! A 0raph of <A vers*s +1, will be a strai0ht line with a slope of &K when <A - (the
observed absorbance! (the initial absorbance! for each point in the titration of 9 with 1(
(c! A 0raph of +91,=+1, vers*s +91, will be a strai0ht line with a slope of &K(
5 of 14
)he method of contin*o*s variation (>ob?s method!
(a! ma' be *sed instead of a 4catchard plot to determine the e7*ilibri*m constant for a
0iven chemical reaction(
(b! ma' be *sed to isolate individ*al components of a m*lti&component s'stem when each
component absorbs at a different wavelen0th(
(c! ma' be *sed to identif' the stoichiometr' of the predominant complex in a s'stem when
several complexes at e7*ilibri*m ma' be present(
# of 14
@hich of the followin0 best describes the application of flow anal'sis;
(a! A sample is inAected into a movin0 li7*id stream to which rea0ents can be added( After
s*itable time, the reacted sample reaches a detector(
(b! A sample is inAected into a movin0 li7*id stream to which rea0ents can be added( After
s*itable time, the reacted sample reaches a detector( )his process enables replicate
meas*rements to be completed rapidl' (e(0( $0 to #0 seconds!(
(c! A sample is inAected into a movin0 li7*id stream to which rea0ents can be added( After
s*itable time, the reacted sample reaches a detector( )his process enables replicate
meas*rements to be completed rapidl' (e(0( $0 to #0 seconds!( 8n addition, different flow
paths ma' be assembled to allow man' different t'pes of anal'sis to occ*r on the same
sample(
/ of 14
@h' are infrared spectra c*stomaril' recorded on a transmittance scale rather than an
absorbance scale;
(a! eca*se the anal'tical application of infrared spectra allows percent transmittance to be
plotted a0ainst the concentration of the anal'te to prod*ce a strai0ht line(
(b! eca*se the transmittance scale allows the pea6 to appear below the baseline rather
than above the baseline of the 0raph(
(c! eca*se wea6 and stron0 bands can be displa'ed on the same scale(
8 of 14
Cramer?s r*le is a method *sin0 determents to solve sim*ltaneo*s e7*ations(A constant B is
divided into individ*al matrices that have been 0enerated from the coefficients of the
e7*ations( Civen the followin0 three sim*ltaneo*s e7*ations,x : ' : "3 - 0, $x ' : $3 - $,
and x : $' : 43 - &1, the val*e of x wo*ld be represented b'D
A(
E0 1 "E
E$ &1 $E
E&1 $ 4E
FFFFFFFFFFFF- x
E1 1 "E
E$ &1 $E
E1 $ 4E
(
E1 1 " E
E$ &1 $E- x
E1 $ 4E
C(
E1 0 " E
E$ $ $ E
E1 &1 4E
FFFFFFFFFFFF- x
E1 1 " E
E$ &1 $E
E1 $ 4E
. of 14
G*minescence is *sef*l in anal'tical chemistr' beca*se
(a! molec*lar ox'0en does not interfere with the emittin0 species enablin0 l*minescence
meas*rements in the field to be ta6en easil'(
(b! si0nals obtained from the anal'te are s*fficientl' lar0e and do not re7*ire amplification(
(c! G*minescence is *sef*l beca*se the intensit' is proportional to the concentration to the
emittin0 species if concentrations are low eno*0h(
10 of 14
@hen meas*red in a 1(00 cm c*vet, a 8(50 x 10
&5
% sol*tion of species A exhibited
absorbances of 0(1$. and 0(/#4 at 4/5 nm and /00 nm, respectivel'( A 4(#5 1 10
&5
%
sol*tion of species 0ave absorbances of 0(5#/ and 0(08" at 4/5 nm and /00 nm,
respectivel'( oth species were dissolved in the same solvent, and the solvent?s absorbance
was 0(005 and 0(000 at 4/5 nm and /00 nm, respectivel'( @hich expressions are correct;
(a! Hor species AD A4/5 nm - 0(1$4 and A/00 nm - 0(/#4
(b! Hor species AD A4/5 nm - 0(1$. and A/00 nm - 0(/#4
(c! Hor species AD A4/5 nm - 0(1$. and A/00 nm - 0(/5.
11 of 14
@hen meas*red in a 1(00 cm c*vet, a 8(50 1 10
&5
% sol*tion of species A exhibited
absorbances of 0(1$. and 0(/#4 at 4/5 nm and /00 nm, respectivel'( A 4(#5 1 10
&5
%
sol*tion of species 0ave absorbances of 0(5#/ and 0(08" at 4/5 nm and /00 nm,
respectivel'( oth species were dissolved in the same solvent, and the solvent?s absorbance
was 0(005 and 0(000 at 4/5 nm and /00 nm, respectivel'( Calc*late the molar
absorptivities for species A(
(a! I4/5 nm - 8.88 cm
&1
%
&1
and I/00 nm - 145. cm
&1
%
&1
(b! I4/5 nm - 1518 cm
&1
%
&1
and I/00 nm - 8.88 cm
&1
%
&1
(c! I4/5 nm - 145. cm
&1
%
&1
and I/00 nm - 8.88 cm
&1
%
&1
1$ of 14
@hen meas*red in a 1(00 cm c*vet, a 8(50 x 10
&5
% sol*tion of species A exhibited
absorbances of 0(1$. and 0(/#4 at 4/5 nm and /00 nm, respectivel'( A 4(#5 1 10
&5
%
sol*tion of species 0ave absorbances of 0(5#/ and 0(08" at 4/5 nm and /00 nm,
respectivel'( oth species were dissolved in the same solvent, and the solvent?s absorbance
was 0(005 and 0(000 at 4/5 nm and /00 nm, respectivel'( Calc*late the molar
absorptivities for species (
(a! I4/5 nm - 1$,1.4 cm
&1
%
&1
and I/00 nm - 1/85 cm
&1
%
&1
(b! I4/5 nm - 1$,08# cm
&1
%
&1
and I/00 nm - 1/85 cm
&1
%
&1
(c! I4/5 nm - 1/85 cm
&1
%
&1
and I/00 nm - 1$,08# cm
&1
%
&1
1" of 14
@hen meas*red in a 1(00 cm c*vet, a 8(50 x 10
&5
% sol*tion of species A exhibited
absorbances of 0(1$. and 0(/#4 at 4/5 nm and /00 nm, respectivel'( A 4(#5 1 10
&5
%
sol*tion of species 0ave absorbances of 0(5#/ and 0(08" at 4/5 nm and /00 nm,
respectivel'( oth species were dissolved in the same solvent, and the solvent?s absorbance
was 0(005 and 0(000 at 4/5 nm and /00 nm, respectivel', in either a 1 or 1($5 cm c*vet(
@hat is the correct expression for a mixt*re of A and , if the sol*tion 'ielded the followin0
absorbance data in a 1($5 cm c*vetD 0(50$ at 4/5 nm and 0(.1$ at /00 nm(
(a! At 4/5 nmD (0(4./!=1(00 cm - (145. cm
&1
%
&1
cA! : (1$,08# cm
&1
%
&1
c! At /00 nmD
(0(.1$!=1(00 cm - (8.88 cm
&1
%
&1
cA! : (1/85 cm
&1
%
&1
c!
(b! At 4/5 nmD (0(50$!=1(00 cm - (145. cm
&1
%
&1
cA! : (1$,08# cm
&1
%
&1
c! At /00 nmD
(0(.1$!=1(00 cm - (8.88 cm
&1
%
&1
cA! : (1/85 cm
&1
%
&1
c!
(c! At 4/5 nmD (0(4./!=1($5 cm - (145. cm
&1
%
&1
cA! : (1$,08# cm
&1
%
&1
c! At /00 nmD
(0(.1$!=1($5 cm - (8.88 cm
&1
%
&1
cA! : (1/85 cm
&1
%
&1
c!
14 of 14
@hen meas*red in a 1(00 cm c*vet, a 8(50 x 10
&5
% sol*tion of species A exhibited
absorbances of 0(1$. and 0(/#4 at 4/5 nm and /00 nm, respectivel'( A 4(#5 x 10
&5
%
sol*tion of species 0ave absorbances of 0(5#/ and 0(08" at 4/5 nm and /00 nm,
respectivel'( oth species were dissolved in the same solvent, and the solvent?s absorbance
was 0(005 and 0(000 at 4/5 nm and /00 nm, respectivel', in either a 1 or 1($5 cm c*vet(
Calc*late the concentrations of A and in a sol*tion that 'ielded the followin0 absorbance
data in a 1($5 cm c*vetD 0(50$ at 4/5 nm and 0(.1$ at /00 nm(
(a! c - /(#5 x 10
&5
%olar and cA - $("/ x 10
&5
molar
(b! c - $("/ x 10
&5
molar and cA - /(#5 x 10
&5
molar
(c! c - 4(#5 x 10
&5
molar and cA - 8(50 x 10
&5
molar