anthranilates with dichloramine-tshodhganga.inflibnet.ac.in/bitstream/10603/62323/10... · nation...
TRANSCRIPT
CHAPTER V
D~ERMINATION OF ANTHRANILIC ACID AND ~AL
ANTHRANILATES WITH DICHLORAMINE-T
The successful application of dibromamine-T in
acetic acid as an oxidimetric titrant for the determi-
nation of anthranilic acid and metal antr~anilates
prompted us to examine the feasibility of employing di
chloramine-T (the chlorine analogue of dibromamine-T) in
this context. Dicr~oramine-T has been introduced as an
'd' .. .,. ., . Ii 42-46 1ox~ ~me~r~c ~~~ran~ oy ear er workers in our a-
boratories. The full list of substances determined by
dichloramine-T titrations is given in Table 1.
The present studies showed that dichloramine-T may
be employed instead of dibromamine-T for the determination
of antr~anilic acid and metal antr~anilates in presence of
bromide ions. Neither of these oxidants has advantage over
the other in this context. In fact the course of titrations
was found to be almost identical. This is not surprising
since, in both cases, the oxidant de facto is the bromine
142
produced in situ by the reaction of dibromamine-T or di-
chloramine-T with the bromide ions present. The results of
our studies on dichloramine-T are presented in this chapter.
1EXPERlMENTAL
Using chloramine-T as a starting material dichloramine-T
was prepared by the method of Jacob and Nair46b (vide page 39,
Chapter II). The details of preparation and standardisation
of stock solutions of dichloramine-T in anhydrous acetic acid
have already been given in Chapter II.
Procedure for Eotentiometric titrations
The procedure was identical with that of the dibro-
mamine-T titrations.
Procedure for visual indicator titrations
The procedure was similar to that in the case of the
dibromamine-T titrations.
RESULTS AND DISCUSSION
Some attempts were made to carry out these titrations
in pure acetic acid medium. In such cases, the antt~anilic
acid or metal antt~anilates were dissolved in anhydrous acetic
acid and were titrated with dichloramine-T solutions in acetic
acid. It was shown that visual indicator response in such a
purely nonaqueous medium was very feeble and the titrations
143
could not be carried out. Potentiometric titrations were
also sluggish in such a medium. These difficulties vanished
when water (~5 ml) was added. The best results were obtained
when the titrate was taken in a mixed aqueous acetic acid
medium containing also hydrochloric acid and the titrant was
taken in anhydrous acetic acid medium. The presence of water
in the titrate system increases the dielectric constant and
favours quicker electrode equilibration. On the other hand
the presence of acetic acid in appreciable concentrations
(~20%) prevents the precipitation of tribromo anthranilic
acid. It was observed that if no acetic acid is taken along
with the titrate, some tribromoantr~anilic acid would get
precipitated; this would adhere to the electrode and cause
complications.
Typical results including statistical data are pre
sented in Tables 67 to 82. Typical titration curves are
given in figures 15 to 21.
The dichloramine-T titrations have the same advantages
as the dibromamine-T titrations (cf page 37) over the con
ventional bromate-bromide excess-back titration procedure.
As mentioned earlier there appears to be no advantage (or
disadvantage) for dicr~oramine-T in this context compared to
dibromamine-T. Thus the dichloramine-T methods may be
regarded simply as a useful alternative to the dibromamine-T
methods.
TABLE 67
DETERMINATION OF ANTHRANILIC ACID WITH DICHLORAMINE-T
(POTENTIOMETRIC TITRATION)
Exp"t.No.
Anthranilicacidmmol
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of ant"hranilic acid.
Anthranilicacidfound*mmol
Error%
------------------------------------------------------------------------------------------1 • 0.1669 0.9980 5.979 0.1663 - 0.36
2. 0.1717 1.028 5.987 0.1713 - 0.23
3. 0.1962 1.189 6.060 0.1981 + 0.97
4. 0.2091 1.257 6.011 0.2095 + 0.19
5. 0.2167 1. 301 6.003 0.2168 + 0.05
6. 0.2455 1.473 6.000 0.2455 0.00
-------------------------------------------------------------------------------------------*Assuming that 6 equivalents of oxidant are consumed per mole
of anthranilic acid. ~
~
"""
TABLE 68
DETERMINATION OF MANGANESE ANTHRANILATE WITH DICHLORAMINE-T
(POTENTIO~RIC TITRATION)
------------------------------------------------------------------------------------------Expt.
No.Manganese anthranilate takenmmol
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tc:onsumed permole of manganesean tt.tXanilat e
Manganeseanthranilatefound*.!a!!!.Q1
Erroroj,,
------------------------------------------------------------------------------------------1- 0.05160 0.6187 11.99 0.05155 - 0.10
2. 0.06250 0.7498 11.99 0.06248 - 0.03
3. 0.07949 0.9590 12.06 0.07991 + 0.53
4. 0.09380 1.125 11.99 0.09375 - 0.05
5. 0.1109 1.329 11.98 0.1107 - 0.18
6. 0.1456 1.748 12.00 0.1456 0.00
*Assuming that 12 equivalents of oxidant are consumed per mole ofmanganese antt.tXanilate.
.......J:>o.U1
TABLE 69
DETERMINATION OF COBALT ANTHRANILATE WITH DICHLORAMINE-T
(POTENTIOMETRIC TITRATION)
Expt. Cobalt antrJaNo. nilate taken
mmol
Dic:hloramine-Tconsumedmeq
Equivalents ofdic:hloramine-Tc:onsumed permole of cobaltanthranilate
Cobaltanthranilatefound*mmol
Error%
---------------------------------------------------------------------------------------1• 0.05090 0.6119 12$02 0.05099 + 0.18
2. 0.06091 0.'7318 12.01 0.06098 + 0.11
3. 0.06'720 0.8069 12.00 0.06'720 0.00
4. 0.0'7933 0.9468 11.93 0.0'7890 - 0.54
5. 0.09542 1.145 11.99 0.09541 - 0.01
6. 0.10'75 1.292 12.01 0.10'76 + 0.09
---------------------------------------------------------------------------------------*Assuming that 12 equivalentsof oxidant are consumed per mole of
cobalt antrJanilate.-'~0'\
TABLE 70
DETERMINATION OF COPPER .ANTHR.ANILATE WITH DICHLORAMINE-T
(POTENTIOMETRIC TITRATION)
Expt.No.
Copper antr.lXanilate taken~
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of copperantru-anilate
Copper antrJIanilate found*mmol
Erroro;~
1• 0.07702 0.9275 12003 0.0772'9 + 0.35
2. .0.08156 0.9787 12.00 0.08156 0.00
3. 0.1063 1.285 12.09 0.1071 + 0.75
4. 0.1158 1.384 11.96 0.1154 - 0.35
5. 0.1322 1.586 11-.99 0.1321 - 0.08
6. 0.1437 1.725 12.0~ 0.1439 + 0.14
---------------------------------------------------------------------------------------------*Assuming that 12 equivalents of oxidant are consumed per mole of
copper anthranilate.
-'~
--J
TABLE 71
DETERMINATION OF NICKEL ANTHRANILATE WITH DICHLORAMINE-T
(POTENTIOMETRIC TITRATION)
Expt. Nickel anttJaNo. nilate taken
mmol
Dichloramine-Tconsumedmeq
Equivalents ofdichloramine-Tconsumed permole of nickelanthranilate
Nickelanthranilatefound*.!!U!!2l
Error%
-----------------------------------------------------------------------------------------1• --'0.05912 0.7091 11.99 0.05909 - 0.05
2. 0.07023 0.8431 12.00 0.07023 0.00
3. 0.08151 0.9789 1?01 0.08157 +0.07
4. 0.09'790 1.1'70 11.95 0.09750 -0.41
5. 0.1066 1.279 11.99 0.1065 -0.09
6. 0.1121 1.343 11.98 0.1119 -0.18
------------------------------------------------------------------------------------------
*Assuming that 12 equivalents of oxidant are consumedper mole of nickel anthranilate. .....
~(Xl
TABLE 72
DETERMINATION OF ZINC ANTHRANILATE WITH DICHLORAMINE-T
(POTENTIO~ffiTRIC TITRATION)
-----------------------------------------------------------------------------------------Expt.
No.Zinc anthranilate takenmmol-
Dichloramine-Tconsumedmeg
EqUivalents ofdichloramine-Tconsumed permole of zincanthranilate
Zincantr.tXanilatefound*mmol-
Error%
----------------------------------------------------------------------------------------1• 0.05721 0.6859 11.98 0.05715 - 0.10
2. 0.06456 0.7747 11.99 0.06455 - 0.01
3. '0.08143 0.9788 12.02 0.09783 + 0.24
4. 0.1047 1.254 11.97 0.1045 - 0.19
5. 0.1122 1.347 12.00 0.1122 0.00
6. 0.09760 1.174 12002 0.09783 + 0.24
----------------------------------------------------------------------------------------*Assuming that 12 eqUivalents of oxidant are consumed per mole of
zinc antr~anilateo
---Po'..0
TABLE 73
DET~IINATION OF CADMIID~ ANTHRANILATE WITH DICHLORAMINE-T
(POTENTIOMETRIC TITRATION)
Expt.No.
Cadmiumanthranilatetakenmmol-
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of cadmiumantliranilate
Cadmiumantr-!Xanilatefound*mmol
Error%
1• 0.05900 0.7072 11.98 0.05893 - 0.12
2. 0.07220 0.8674 12.01 0.07228 + 0.11
3. 0.09551 1.146 11.99 0.09550 - 0.01
4. 0.1021 1.223 11.97 0.1019 - 0.19
5. 0.1144 1.382 12.0$ 0.1151 + 0.61
6. 0.1322 1.589 12.02 0.1324 + 0.15
---------------------------------------------------------------------------------------*Assuming that 12 equivalents of oxidant are consumed per mole of
cadmium anthranilate.
~
IJIo
TABLE 74
STATISTICAL DATA FOR TITRATIONS WITH DICHLOF~INE-T
(POTENTIOMETRIC TITRATIONS)
------------------------------------------------------------------------------------------Reductant No. of experi
ments doneRelative meandeviation
Standarddeviation
Coefficient ofvariati••
Anthranilicacid
Manganeseanthranilate
Cobalt anttJXanilate
Nickel anthranilate
6 0.3097
6 0.1600
6 0.1700
6· . 0.1201
4.686x10-3
2.537x10-3
2.578x10-3
1.691x10:3
0.4681
0.2537
0.2579
0.1693
Copper anttJXanilate
Zinc: anthranilate
Cadmium anthranilate
6
6
6
0.2698
0.1400
0.1900
3.806x10-3
1.766x10~3
2.851x10-3
0.3802
0.1766
0.2851
--------------------------------------------------------------------------------------------->\J1->
-----_._-_._..-.....-
ANTHRANILIC ACID V. D'CH::R-A-~'NE~_·····-l
152
lOCO
:e~900wM~ 800
'"eai 700
000
3500 1000>E
3000 '~900> w<l u-.. IIIW
500 <l ~eoo
&t-e2000 Ii 7
3500
·3000
>"~
. 2S00'"<l
2000
600
500
ISOO
1000
600
500
1500
1000
400
:---;;';---+---=.-f;;--.;-----*----~4 4.5 5 5.5 6 6.5VOLUM! Of DICHLORAMINE _TIN mt.
FIG.IS
500 400
7VOLUME OF DICHLORAMINe_T IN mi.
FIG.16
10
500
COBALT ANTHRANlLAtf V. DICHLORAMINf _t NICKfL ANTHRANILATE V. DICHLORAMINE.T
>1000E
~w900:;l
:!! 800..,Eoj
700
600
500
400
4.5 5.5VOLUME OF DICHLORAMINE-T IN mi.
FIG. I?
1000l
3500 ilE 900~III
3000> ~BOO<I ......... Ew Ii
00<1 700
600
1500 500
1000 400
SOO 300
4.S 5 5.5 6 6.5 f
VOLUME Of DICHLORAMINE. T IN mi.FIG. Ie
7.S
4000
3500
~000><l
"'SOO ':1
2000
ISOO
1000
500
COPPER ANTHRANILATE Va DICHLORAMINE.T
153
ZINC ANTHRANILATE' V. DICHLORAMINE _T
3500~
1000
~9003000 tJ
> III<l
~2500 ";0- 800<l ""E
~O";700
1500 600
> 1000e
;>;w 900uen
~ 800...Ew 700
600
500
400
5.5 6 6.5 7 7.5 8VOLUME OF DICHLORAMINE _TIN mI.
Ft<i. 19
8.5
1000
500
500
400
7 'l5 8 8.5 9 9.3VOLUME 01' DICHLORAMINE _TIN mi.
Fili. 20
3000
~w
2500 <l
2000
500
100
l2: "'00L1I
:ll 800~
t 700oj
600
soo
CADMIUM ANTHRANILATE V. DICHLORAMINE.T
3500
3000~';;i-
500 '4
2000
1500
1000
'100
8 8.5j -,--,---;t'
9 9·5 10 10:5- IIVOLUME OF DICHLORAMINE.T IN ml.
FIG.21
TABLE 76
DETERMINATION OF ANTHRANILIC ACID WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
Expt. AntrJanilicNo. acid taken
.!1!!2!
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed per.mole of antrJanilic acid
Anthranilic acidfound*~
Error Indicator%
--------------------------------------------------------------------------------------1 • 0.1468 0.8780 5.980 0.1463 -0.34 Quinoline
yellow.
2. 0.1507 0.9008 5.977 0.1501 -0.40 "
3. 0.1782 1.069 5.998 0.1781 -0.06 "
4. 0.1891 1.137 6.012 0.1895 +0.21 \I
5. 0.1990 1.201 6.035 0.2001 +0.55 "
6. 0.2233 1.343 6.014 0.2238 +0.22 "----------------------------------------------------------------------------------------*Assuming that 6 equivalents of oxidant are consumed per mole ofantr~anilic acid.
->\5!..p.
!ABLE 76
DETERMINATION Oli' WlANGANESE ANTHRANILATE WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
Expt.No.
Manganeseantb.ranilatetakenm!!!.Q1
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of manganese anthranilate
ManganeseanttJI'anilatefound*:!!!!!1.21
Error%
Indicator
------------------------------------------------------------------------------------------1• 0.04912 0.5887 11.99 0.04-905 -0.14 Quinoline
yellow.
2. 0.06050 0.7198 11.89 0.05998 -0.86 II
3. 0.07739 0.9290 12.00 '0.07741 -1-0.03 "
4. 0.09180 1.096 11.93 0.09133 -0.51 II
5T 0.1008 1.216 12.06 0.1013 +0.50 "
6. 0.1314 1.590 ~,2.10 0.1325 +0.84- ".,
------------------------------------------------------ ----~-------------------------------
*Assuming that 12 equivalents of oxidant are consumed per mole ofmanganese anthranilate.
-"ViVi
TABLE 77
DETERMINATION OF COBALT ANTHRANILATE WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
Expt. Cobalt antr~a
No. nilate takenmmol..............
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of cobaltanthranilate
Cobalt anthranilate found*mmol
Error%
Indicator
------------------------------------------------------------------------------------------1• 0.04980 0.6009 12.06 0.05007 + 0.54 Quinoline
yellow.
2. 0.05971 0.7200 12.05 0.06000 + 0.49 11
3. 0.06610 0.7909 11.96 0.06590 - 0.30 11
4. 0.07831 0.9360 11.95 0.07800 - 0.40 "
5. 0.09971 1.197 12.00 0.09971 - 0.00 11
6. 0.1075 1.286 ~"1. 96 0.1071 - 0.37 11
--------------------------------------------~---------~------------------------------------
*Assuming that 1~ ~quivalents of oxidant are consumed per mole ofcobalt antr~anilate.
-"\.J10'1
TABLE 78
DETERMINATION OF NICKEL ANTHRANILATE WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
Expt.No.
Nickelanthranilatetaken.!!!!!!2!
Dichloramine-Tconsumedmeq
Equival en ts ofdichloramine-Tconsumed per mciieof nickel anthranilate
Nickelanthranilatefound*mmol
Error%
Indicator
-----------------------------------------------------------------------------------------1. 0.05812 0.6952 11.96 0.05793 -0.33 Quinoline
yellow.
2. 0.06920 0.8301 11.99 0.06917 -0.04 "3. 0.08045 0.9669 12.01 0.08057 +0.15 "4. 0.08900 1.065 11.96 0.08875 -0.28 "
5. 0.09460 1.142 12.07 0.09516 +0.59 "6. 0.1041 1.243 11.94 0.1035 -0.58 "
------------------------------------------------------------------------------------------*Assuming that 12 equivalents of oxidant are consumed
per mole of nickel anthranilate.~
IJl--:l
TABLE 79
DETER~INATION OF COPPER ANTHRANILATE WITH DICHLORAMIN~T
(DIR~T TITRATION USING VISUAL INDICATOR)
-----------------------------------------------------------------------------------------------I
Expt. Copper antrJaNo. nilate taken
mmol
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of copperanthranilate
CopperantrJXanilatefound.!ill!!21
Error%
Indicator
------------------------------------------------------------------------------------------------
2. 0.08049 0.9666 12.01
3. 0.09108 1.0993 12.0,
4. 0.1057 1.265 11.97
5. 0.1200 1.428 11.90
60 0.1327 1.599 12.05
1 • 0.07600 0.9158 12.05 0.07637 + 0.49 Quinolineyellowo
0.08056 + 0.09 n
0 009172 + 0070 "
0.1054 - 0.28 "
0.1190 - 0.83 "
0.1333 + 0.45 n
----------------------------------------------------------------------------------------------
*Assuming that 12 equivalents of oxidant are consumed per mole ofcopper antbranilateo
......\51CD
TABLE 80
DETERMINATION OF ZINC ANTHRANILATE WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
------------------------------------------------------ ---------~~--------------------------
Expt.No.
Zinc ant'hranilic: taken!!l!!1Q1
Dichloramine-Tconsumedmeg
Equivalents ofdichloramine-Tconsumed permole of zincanttlXanilmte
Zinc anttlXa- Error Indicatornilate %found*mmol
-------------------------------------------------------------------------------------------1 • 0.05801 0.6972 12.01 0.05810 + 0.16 Quinoline
yellow.
2. 0.06351 0.7639 12.02 0.06365 + 0.22
3. 0.07115 0.8544 12.00 0.07115 0.00
4. 0.08068 0.9678 11.99 0.OSrOb5 -0.04
5. 0.09060 1.093 12.06 0.09108 +0.53
6. 0.09480 1.134 11.96 0.09450 -0.32
II
II
It
It
-------------------------------------------------------------------------------------------*Assuming that 12 equivalents of oxidant are consumed per mole of
zinc antt~anilate.
-'\J11..0
TABLE 81
DETERMINATION OF CADMIUM ANTHRANILATE WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
Expt. CadmiumNo. antr.1Xanilate
taken~
Dichloramine-Tconsumedmeq
Equivalents ofdichloramine-Ifconsumed permole of cadmiumanthranilate
Cadmiumantt.1Xanilatefound*1lli!l.Q1
Error%
Indicator
-------------------------------------------------------------------------------------1• 0.05611 0.6759 12.04 0.05632 +0.37 Quinoline
yellow.
2. 0.07130 0.8564 12.01 0.07136 +0.08 "
3. 0.08240 0.9875 11.98 0.08229 -0.13 "
4. 0.09230 1.100 11.90 0.09166 -0.69 "
5. 0.1034 1.242 12.01 0.1035 +0.10 "
6. 0.1212 1.448 11.94 0.1206 -0.50 "
------------------------------------------------------------------------------------*Assuming that 12 equivalents of oxidant are consumed per
mole of cadmium antr.1Xanilate....0\o
TABLE 82
STATISTICAL DATA FOR TITRATIONS WITH DICHLORAMINE-T
(DIRECT TITRATION USING VISUAL INDICATOR)
------------------------------------------------------------------------------------------Reductant No. of experi
ments doneRelative meandeviation
Standarddeviation
Co efficien t ofvariation
------------------------------------------~---------------------------~-------------------
Anthranilicacid
6 0.2900 3.657x10-3 0.3657
Manganese anttJani1.ate
Cobalt anthranilate
Nickel anthranilate
Copper anthranilate
Zinc anthranilate
Cadmium anthranilate
6 0.4800 6.281x10-3 0.6282
6 0.3500 4.285x10-3 0.4285
6 0.3103 4.137x10-3 0.4141
6 0.4396 5.619x10-3 0.5614
6 0.2100 2.859x10-3 0.2859
6 0.3105 3.994x10-3 0.3999
--------------------------------------------------------------------------------------------->()\
->
162
Inasmuchas both oxine and antt~anilic acid (as well
as their metal complexes) may be oXidimetrically determined
with dibromamine-T and dichloramine-T in presence of bromide,
it seems likely that these methods are capable of being
extended to the determination of organic compounds which are
known to be readily and quantitatively brominated. Each
case will have to be examined in detail before specific
analytical recommendations could be given.