ANTHRANILATES WITH DICHLORAMINE-Tshodhganga.inflibnet.ac.in/bitstream/10603/62323/10... · nation of anthranilic acid and metal antr~anilates ... be employed instead of dibromamine-T

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


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


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


Expt.No.

Copper antr.lXanilate taken~


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


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-


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


Expt.No.

Cadmiumanthranilatetakenmmol-


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!


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


Expt.No.

Manganeseantb.ranilatetakenm!!!.Q1


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


Expt. Cobalt antr~a

No. nilate takenmmol..............


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


Expt.No.

Nickelanthranilatetaken.!!!!!!2!


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


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


------------------------------------------------------ ---------~~--------------------------

Expt.No.

Zinc ant'hranilic: taken!!l!!1Q1


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


Expt. CadmiumNo. antr.1Xanilate

taken~


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


------------------------------------------------------------------------------------------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.

Documents

ANTHRANILATES WITH DICHLORAMINE-Tshodhganga.inflibnet.ac.in/bitstream/10603/62323/10... · nation of anthranilic acid and metal antr~anilates ... be employed instead of dibromamine-T