HYDROXAMIC ACIDS AND THEIR ANALYTICAL

APPLICATIONS

Y X . Agrawal
Pharmacy Department
Faculty of Technology and Engineering
M.S. University ofBaroda
Kalabhavan, Baroda 390001
INDIA

CONTENTS
Page
INTRODUCTION 5
PREPARATION OF HYDROXAMIC ACIDS 6
Properties 7
APPLICATION OF HYDROXAMIC ACIDS IN ANALYTICAL
CHEMISTRY 7
Gravimetric Determinations 7
General Procedure for the Gravimetric Determination 11
Separation and Gravimetric Determination of Rare Earths with
N-m-tolyl-m-nitrobenzo-hydroxamic Acid 11
Separation and Gravimetric Determination of Cerium:
Separation from Common Metal Ions 12
Separation of Cerium from Rare Metals 12
Separation and Gravimetric Determination of Lanthanum,
Praseodymium Neodymium, Samarium and Gadolinium from
Common Metal Ions 12
Separation and Determination of Lanthanum from Rare Metals 13
Separation and Determination of Praseodymium from Rare
Metals 13
Separation and Determination of Neodymium from Rare Metals 13
Separation and Determination of Samarium (III) from Rare
Metals 13
Separation and Determination of Gadolinium (III) from Rare
Metals 13

3
 CONTENTS (cont)

SOLVENT EXTRACTION AND COLORIMETRIC DETERMINATION OF

METALS WITH HYDROXAMIC ACIDS 14
Spectrophotometric Determination of Vanadium 14
General Procedure 15
Spectrophotometric Determination of Titanium 19
Spectrophotometric Determination of Molybdenum with
Benzohydroxamic Acid 21
Spectrophotometric Determination of Cerium with N-phenyl-2-
naphthohydroxamic Acid 21
Spectrophotometric Determination of Uranium (VI) with
N-phenyl-2-naphthohydroxamic Acid 21
Spectrophotometric Determination of Iron (III) with p-Nitro-
benzohydroxamic Acid 22
Spectrophotometric Determination of Niobium with N-phenyl-
benzohydroxamic Acid 22
Non-Aqueous Titrations of Hydroxamic Acids 23
Detection of Hydroxamic Acids 24
REFERENCES 25

4
 INTRODUCTION

The search for specific analytical reagents has led to the use o f a
large number o f organic ligands for complex formation with metal ions.
For the proper evaluation o f analytical methods involving organic
reagents it is necessary to k n o w the nature, specificity, selectivity and
sensitivity o f the reactions with inorganic ions and the solubility and
stability o f the products o f their reactions. Therefore, it is valuable to
pursue the evaluation o f versatile and important analytical methods.
Organic reagents b y their ease o f substitution o f t e n a f f o r d reagents o f
desired analytical properties.
Hydroxamic acids, having the bidentate functional grouping (I),
fulfil the basic requirement o f complex formation with metal ions and,
therefore, f o r m an important family o f chelating agents.

— Ν OH

— C = 0

(I)

Structurally, hydroxamic acids can be represented in their t w o tauto-

meric forms (II) and (III).

Η — N — O H N—OH Rj — Ν — O H
I I! I
R — C = 0 R — C — O H R — C = 0
(II) (III) (IV)

By substituting the hydrogen atom attached to the nitrogen atom in (II)

b y alkyl or aryl groups, numerous N-substituted h y d r o x a m i c acids o f
type (IV) can be obtained.
The complex formation o f hydroxamic acids o f t y p e ( I V ) usually
takes place with the replacement o f the h y d r o x y l a m i n e hydrogen b y
the metal ion and ring closure through the carbon o x y g e n .

R , — N — O H

R — C = 0
[ R , — ΝΝ — 0 \

R1 — C
I
I „
M + nHT

5
 T h e metal chelates o f hydroxamic acids are non-ionic in nature.
T h e r e f o r e , it is possible to extract these uncharged metal chelates or
inner complexes with water immiscible solvents. The coloured and
stable solutions o f these complexes o f t e n provide photometric methods
for the determination o f several metal ions. A t the same time, the water-
insoluble and thermally stable metal complexes o f hydroxamic acids
have provided excellent gravimetric methods for the determination o f
various metal ions.

PREPARATION OF HYDROXAMIC ACIDS

Several methods for synthesising hydroxamic acids have been

described b y Yale /1/, and the one mostly used is the partial acylation
o f the appropriate N-aryl ( o r alkyl) hydroxylamine with an acid chlor-
ide, acid anhydride or ester. When an N-arylhydroxylamine reacts with
an acid chloride, both o f its hydrogen atoms, attached to the nitrogen
and o x y g e n atoms, are attacked thereby simultaneously producing
m o n o ( I I ) and d i - ( V ) and o-acyl ( V I ) substituted derivatives

R — Ν — O H + R — C = 0 R — Ν — O H R — Ν — Ο — C O R
+
I I — I I
Η CI R — C = 0 R — C = 0

(II) (V)
R — Ν — Ο — C O R
I
Η HCl
(VI)

and thus tedious methods o f purification, e.g. extraction with ammonia

12, 3/, become necessary. Tandon and co-workers /4-9, 10/ have shown
that purer products in better yields can be obtained if the compounds
are prepared b y slowly adding an exactly equimolar ethereal solution o f
the acid chloride dropwise to a vigorously stirred cold ( 0 ° or b e l o w )
ethereal solution o f N-arylhydroxylamine containing an aqueous sus-
pension o f sodium bicarbonate. The granular precipitate f o r m e d during
the reaction and the solid mass obtained on removing ether at low
pressure are mixed and triturated with saturated sodium bicarbonate
solution to remove acidic impurities. The products, crystallized t w o or
three times f r o m benzene and petroleum ether are satisfactorily pure.
Ethanol-water or dioxan-water mixtures without the use o f charcoal

6
are also recommended for crystallization of N-arylhydroxamic acids
insufficiently soluble in benzene.

Properties
Generally, hydroxamic acids are white solids except for the nitro-
disubsubstituted and iodo-substituted derivatives which are, respectively,
light yellow, pale yellow and light pink in colour. They are weak acids,
though several times stronger than phenol. The dissociation constants
of the hydroxamic acids and their metal ligand stability constants have
been summarized by Agrawal /ll/. The acidity of hydroxamic acids
may be attributed mainly to the OH group and its supression to intra-
molecular hydrogen bonding, as shown by infra-red studies /12, 13/.
The infra-red spectra o f hydroxamic acids show the most characteris-
tic bands associated with the hydroxamic acid functional grouping
( V I I ) to be those due to the ( O - H ) , ( C = 0 ) and ( N - O )

—Ν—OH
I
— c = o
(VII)

stretching vibrations. These frequencies are generally assigned in the

region of 3200 cm" 1 , 1600 cm"1 and 910 cm" 1 , respectively /15-17/.

APPLICATION OF HYDROXAMIC ACIDS IN ANALYTICAL CHEMISTRY

Gravimetric Determinations

Among the most important applications of hydroxamic acids in

analytical chemistry are their uses as precipitating reagents for metal
ions. In most cases, gravimetric determination is possible even in the
presence of other ions by direct weighing without ignition and it is
sometimes possible to separate interfering ions by controlling the pH
and by the use of masking agnets. The substituted hydroxamic acids
most used for the gravimetric determination of various metal ions are
summarised in Table I.
Moshier and Schwarberg /18/ have used N-phenylbenzohydroxamic
acid ( P B H A ) for the determination of tantalum and its separation from
other metal ions. Ellefsen et al /19/ have further substituted the PBHA

7
 TABLE I

Gravimetrie Determination of Metals with Various substituted Hydroxamic Acids

Metal pH of Separated Ref.

precipitation from

I II III IV

1. N-Phenylbenzohydroxamic acid
Al3* 3.6-6.4 Be, Co, Ni, U ( V I ) , Zn, M n 21
Be2+ 5.5-6.5 Fe (III), Al, Ti 22
Bi3+ 6.0-6.8 Fe (III), Ti, W (VI), M o (VI), V (V), 23
A s (V), Pb, A l , Cu, Co, Ni, C d , Hg (II), Pd
6.0-6.8 Mg, As, Sb, M o (VI), W, Be, U (VI) 22
Μη, Co, Ni, Co, Zn, Cd, Hg, Pd
Ce3+ 4-2 Th, U, Ce, F e 2 + , Fe 3 + , Al, Ga, In, S c Zn, Cu, Ni,24
2+
Cd 5.8-6.5 Ag, Be, Pb, Cu, Zn, Hg, Al, Bi, La, Ti, Zr, 24a
V (V), M o , U.
Co2 + 5.5-6.5 Cu 26a
Cu2+ 3.6-6.0 Pb, Hg (II), Cd, Co, Be, Zn, M n , Ni, U (VI), 21
A s (III) & (V)
4.5 Cd, Co 19
Fe3+ 3.0-5.5 Co, Ni, Mn, U (VI), Z n 21
Ga3+ 2.0-3.0 Al, C u , T h , C e ( l l l ) , Ti, U ( I V ) , In, Be, 27,28
Fe (II), Z n
Hg2+ 3.0-6.0 Zn, Co, Ni, Pb. A g . T l ( l ) , B i . S b ( I V ) , Cd, In 29
A s (V), W (VI), M o ( V I )
ln3+ 4.3-8.0 Fe (III), Cu, Zn, Sn, Ni, Ca 27
La3+ 6.4-7.2 U (VI), Ce (IV), Fe (II) (III), A l , Ga, In, Sc, 30
Zn, C u , N i , Th.
Mg2+ 8.0 Be, Cu, Ni. Co, Zn. Al, F e ( l l l ) , T h 31
Mo (VI) 0.01-2.5 Cu, Co, Ni, Fe. V (V), Cr (IV) 32.33
I M HCl
N b !V) 10%H2S04 Zn, Mn, Ni. Co, Cu, Cd, Hg. Be, Mg. U (VI). 34,35
Cr (III), Fe (III), Al, Ce (III), A s (III), Th, PO^ 36.37
Ni2+ 5.5-6.5 Cu 26a
Sc3+ 5.4 Zr and rare earths 39
S n (II) & 0.1 - 0 . 5 Μ Cu, Pb, Z n 40
(IV) HCl
Ta (V) 0.0-1.5 Ti, Zn, N b 18,35,38
21
T h (IV) 4.0-8.5 La, Ce (III), rare earths, Ti, Zr, Ga, In, 63,41,42
Fe (III), A l , V (V), U (VI)
Ti(IV) 0.12-0.5M M o (VI), Th, Ce (III), V (V), Fe (II), Zn, Cu 35.43-45
HCl

8
 T A B L E I (cont.)

I II III IV

U(VI) 5.2 - 5.6 Pb, Bi, Fe (III), Ti, Zn, Mo (VI) 46

Ce (III), Al, T h
0 . 5 - 1.0 Μ Mo (VI), U (IV), Ti, Fe (III), V (VI)
HCl
W(VI) 0 . 0 5 - 1.0 Μ 47
HCl 38
Zr4+ 0.5-0.6Μ Cu, Al, Bi, Cd, Cr (I II) 48
HCl
2.4 Μ HCl Pb, Mg, Mn, Ni, Zn
1.8M,H2S04 Th, Sm, La, Pr, Gd, Ti, Nb, Ta, V (V)
Zn2+ 5.3 - 6.8 Ca, Sr, Ba, Mg, In (II), Be, Hg(l), Cd, 64
As (IV), S b (IV), Mo (IV), W (IV),
La (III), U (VI)

2. N-O-Tolylbenzohydroxamic acid
Bi3+ 6.0 -®.0 Mg, As, Sb, Mo, WO 2 ", Be, Pb, La, Th, 62
U O 2 , Mo, Co, Ni, Cu, Zn, Cd, Mg, Pd
Nb (V) 4.5-6.0 Cr (III), Be, Mg, Cd, Al, La, 49
Ce (III), Se
Ta (V) 1-1.8 Th, U, Co, Ni, Cu, Hg (II), Zn, PO 3 " 33

3. N-Phenyl-2-thiobenzohydroxamic acid
Cu2+ 2.0-2.5 Fe (III), Al, Ni, Co, Zn, Sb, Bi, Pb, Sn 50

4. N-Phenyl-cinnamohydroxamic acid
Nb (V) 7.5 Zn, Mn, Ni, Co, Mg, Be, Cu, Hg (II), 51
Cd, As (III), Bi
Ta (V) 2.5 Al, Cr (III), U (VI), Th, Ce (IV) 52

5. N-Phenyl-Salicylohydroxamic acid
Ti (IV) 6.6 Th, Cu, Be, Zn, Mn, Al, Cd, Hg, Fe (II) & (III) 52

6. Ν - Phenyl-O-nitrobenzohydroxamic acid
Th (IV) 4 . 0 - 4 . 5 Mn, Ni, Ga, Be, Pb, Al, Sn, Sb, La, Mo, Ti, 53
Zr, U

7. N-m-Tolyl-m-nitrobenzohydroxamicacid
Ba2+ 2.5 - 3 0 Ag, Mn, Cu, Ni, Cd, Zn, Hg, Pd, Be, Ga, S b 54
As, Bi, Ti, Zr, V (V), Mo (VI), U O * > r , Nd,Sm
 T A B L E I (cont.)

I II III IV

7. N - m - T o l y l - m - n i t r o b e n z o h y d r o x a m i c acid (cont.)
Be 2 + 7.9-8.9 Ag, Pd (II). Μη, Ni, Zn, Cu, Hg, Ga, Sb, As, 55
Bi, T i , Sr
Ce (IV) 3.8-4.1 Ag, Pd (II), Mn, Ni, Zn, Cu, Hg, Ga, Sb, As, 55
Bi, Ti, Zr.
Ce 3 + 6.0-6.8 Common metals, Th, U, La, Pr, Nd, Sm, Gd 26
La 3 * 7.5-8.5 Common metals, Th, U, Ce, Pr, Nd, Sm, Gd 26
Pr 3 + 8.6-9.2 Common metals, Th, U, Ce, Nd, La, Sm, Gd 26
Nd3+ 8.8-9.5 Common metals, Th, U, Ce, La, Pr, Sm, Gd 26
Sm3+ 9.6-10.2 Common metals, Th, U, Ce, La, Pr, Nd, Gd 26
Gd3+ 10.3 - 10.5 Common metals, Th, U, Ce, La, Pr, Nd 26

8. N - Phenyl-acetylsalicylohydroxamic acid
Ti(IV) 1-2MHCI Co, Ni, Cr, Sb, Hg, Be, C e ( I V ) , Zr, T h , 56
U(VI), U

9. Salicylohydroxamic acid
Al3+ 6-7.5 Be, Co, Ni, U (VI), Zn, Mn 57
Ga 3 + 5.5-6.5 Cu, Th, Ce (III), T i , U (VI) 57
ln3+ 4.5-5.0 Fe ( I I I ) , Cu, Zn, Sn, Ni, Pd 57

10. Quinaldinohydroxamic acid

Nb (V) 3.8-5.0 Ta, Fe (III), U (VI), Be, Th, rare earths, Cu, Cd, 58
Bi
Ta (V) 4-6.8 Zn, Mn, Ni, Co, Cu, Cd, Hg (II), Be, Mg, Al, 58
Ce(lll)

11. Phenylacetohydroxamic acid

Nb (V) 4.0-6.4 Fe (III), Ce (III) rare earths 59
Ta (V) 4.5-6.2 Zr, rare earths, T i , Ga, In 59

12. N - P h e n y l - N - t h i o b e n z o h y d r o x a m i c acid
Fe3* 3-5 Co, Ni, Mn 60

13. N - p - C h l o r o p h e n y l - m - n i t r o b e n z o h y d r o x a m i c acid
Ce 3 + 7.2 - 8.0 Common metals and rare metals 61
Gd3+ 10.5-10.8 Common metals and rare metals 61
La3+ 6.2 - 7.0 Common metals and rare metals 61
Nd3+ 8.7-9.3 Common metals and rare metals 61
Pr 3 + 8.5-9.0 Common metals and rare metals 61
Sm3+ 9.5 - 10.0 Common metals and rare metals 61

10
molecule for use in precipitation of metal ions from homogeneous
solutions and described the use of PBHA-acetate for homogeneous
precipitation of copper. Belcher, Wilson and West /20/ have described
many useful gravimetric determinations of metal ions with PBHA and
this constitutes an important reference. Shome et al. /21/ have investi-
gated the use of PBHA as a metal precipitant and its use has been further
discussed by Majumdar in his monograph /22/ and by Bhura /23/ in a
technical note for the first time. Recently, Agrawal et al have described
the use of N-m-tolyl-m-nitrobenzohydroxamic acid for the quantitative
determination and separation of rare earths and other metal ions /24-26/.

General Procedure for th,e Gravimetric Determination

In a 1L. pyrex beaker, take 10 ml of solution of metal ion (about 0.5
mg) in 500 ml of distilled water and heat it to 60°C on a water bath.
Add ca 20 ml of a 0.1 Μ solution of hydroxamic acid in ethanol with
constant stirring followed by 0.1 Μ ammonia solution until complete
precipitation is achieved. (Adjust the pH of precipitation with ammon-
ium chloride). Digest the granular complex thus obtained for 30 min.
on a water bath, filter through a No. 4 sintered glass crucible, wash
thoroughly with hot water and finally with 20% aqueous ethanol (10 χ
10 ml). Dry the complex at 110°C and weigh it directly.

Separation and Gravimetric Determination of Rare Earths with N-m-

tolyl-m-nitrobenzo-hydroxamic acid
The separation and gravimetric determination of Ce 3+ , La 3 + , Pr 3 + ,
Nd 3 + , Sm 3 + and Gd 3 + in the presence of several foreign ions may be
prepared as follows.
In a 1L. beaker, a saturated solution of the metal ion and about 500
ml of distilled water are heated to 60°C on a water bath. About 20 ml
of reagent solution (N-m-T-m-NBHA) in ethanol are added dropwise
with constant stirring followed by 0.1M ammonia solution until the
precipitation is complete. The pH is adjusted for the precipitation of
various rare earths by ammonium chloride (0.1M):

metal pH of precipitation
Ce 3 + 6.0-6.8
La 3 + 7.5-8.5
Pr 3 + 8.6-9.2
Nd 3 + 8.8-9.5
Sm 3 + 9.6 - 1 0 . 2
Gd 3 + 10.3 - 10.5

11
The granular complex thus obtained is digested for about 30 min.,
filtered through a No. 4 sintered glass crucible. The precipitate was
washed thoroughly first with hot water and finally with 20% aqueous
ethanol (10 χ 10 ml).
For microgram amounts the contents were centrifuged for 3 min.
and after washing etc., filtered through a fine porosity weighed filter
paper and mounted on a weighed steel planchette. The solid com-
plexes thus obtained were dried at 110°C and weighed directly as
(C14MuN204)M.

Separation and Gravimetric Determination of Cerium: Separation from

Common Metal Ions
A known amount of the foreign metal ion is added to the Ce (III)
solution and the latter is diluted to about 500 ml. The pH is adjusted
to 6.0-6.8 with 0.01M ammonia solution and 0.01M H N 0 3 . 10 ml of a
1% solution of KCN are added and the contents are heated to 60°C on
a water bath and the precipitation carried out as before with constant
stirring. The cerium (III) may be separated from and determined in the
presence of A g \ Mn 2 t , Cd 2 + , Hg2 + or G a 3 \ Cerium may be separated
from Pb 2 + , Pd 2+ , Be2*, Sb 3 + , Sn (II), Bi 3+ , Zr (IV) and Ti (IV) with
10 ml of 1% solution of citrate or oxalate instead of cyanide solution.

Separation of Cerium from Rare Metals

Cerium (III) may be separated from Th (IV), U (VI) and Ce (IV) by
precipitating these ions at pH 3.8 to 4.8, and then Ce (III) may be re-
precipitated from the mother liquor at pH 6.0-6.8. La3*, Pr 3+ , Nd 3+ ,
Sm 3 + and Gd 3 + form complexes with N-m-T-m-NBHA at pH > 7.5 and
thus their interference may be eliminated.

Separation and Gravimetric Determination of Lanthanum, Praseody-

mium Neodymium, Samarium and Gadolinium from Common Metal
The separation and determination of La, Pr, Nd, Sm or Gd may be
effected by masking the common metals as described for cerium.
La, Pr, Nd, Sm or Gd may also be separated from Ag+, Cu 2+ , Pb 2+ ,
Zn \ Fe 3 Al 3 Ce 3 Bi3 Cd 2 + and Mg2 + by precipitating these below
2

pH 6.5 with an excess of N-m-tolyl-m-nitrobenzohydroxamic acid. The

precipitate is filtered, washed and dried and La, Pr, Nd, Sm or Gd are
precipitated at the appropriate pH from the mother liquor.

12
Separation and Determination of Lanthanum from Rare Metals
Lanthanum may be separated from Th (IV), U (VI) and Ce (IV) by
precipitating these ions at pH 3 . 8 4 . 8 and the La (III) may be precipita-
ted from the mother liquor at pH 7.5-8.5. Pr 3 *, Nd 3 + , Sm 3 + and Gd 3 +
form their complexes at pH 8.5 and do not interfere with the deter-
mination of La (III).

Separation and Determination of Praseodymium from Rare Metals

Praseodymium (III) may be separated from Th (IV), U (VI) and
Ce (IV) by precipitation at pH 3.84.8 with N-m-T-m-NBHA and sub-
sequently Pr (III) is precipitated from the mother liquor at pH 8.6-9.2.
Praseodymium (III) can be determined in the presence of La 3 + by
precipitating La at pH 7.5-8.5 and subsequently raising the pH to 9.6.
Pr 3 + may be partially separated from Nd 3 + because Nd 3 + also precipi-
tates between pH 8.8-9.5. However, 90-95% separation can be obtained
by carefully adjusting the pH to 8.3-9.3 and by fractionally crystallizing
the Pr complex from ethanol; the Pr complex is more soluble than that
of Nd 3 + .

Separation and Determination of Neodymium from Rare Metals

Neodymium (III) can be separated from Ce (IV), thorium (IV) and
uranium (VI) by precipitating these at pH between 3.8 and 4.8 and
subsequently raising the pH to 8.8-9.6.
Nd can be separated from La 3 + and determined by precipitating
La (III) at pH 7.5-8.5 and then precipitating the Nd from the mother
liquor. Sm 3 + and Gd 3 + do not interfere because the pH for precipitation
of these ions is higher than that for Nd 3 + . The separation from Pr 3 +
can be done partially by taking advantage of the greater solubility of
the Pr complex in ethanol.

Separation and Determination of Samarium (III) from Rare Metals

Sm 3 + may be separated from Ce (IV), Th (IV) and U (VI) by adjus-
ting the pH of the solution to 2 . 8 4 . 8 with N-m-T-m-NBHA and sub-
sequently raising th£ pH to 9.6-10.2 to precipitate the Sm (III). Similar-
ly, Sm may be determined in the presence of La (III), Pr (III) and
Nd (III) by precipitating these at pH 7.5-9.5 and then raising the pH
for Sm (III) precipitation.

Separation and Determination of Gadolinium (III) from Rare Metals

Gd 3 + was determined in presence of Th (IV) and U (VI) by precipi-

13
tating them at pH 3.84.8 and then the Gd ( I I I ) at pH 10.3-10.5. Gd 3 +
may be separated and determined in the presence o f La ( I I I ) which is
precipitated at pH 7.5-8.5; Pr 3 + , N d 3 + and S m 3 + d o not interfere with
the precipitation o f Gd because they precipitate at the lower pH (8.5-
10.2).

SOLVENT EXTRACTION AND COLORIMETRIC DETERMINATION

OF METALS WITH HYDROXAMIC ACIDS

The potentialities o f the metal chelates o f hydroxamic acids as ex-

tractants have been fully recognised during the last two decades and
some very useful separations and extractions have been achieved. A
brief review is given in Table II. Dryssen /65/ was the first to study the
solvent extraction behaviour o f PBHA complexes o f uranium ( V I ) ,
thorium ( I V ) and lanthanum ( I I I ) . The optimal extraction pH values
for the PBHA complexes o f several metals have been compiled by
Shendrikar /66/.
P B H A has also been employed for the extraction o f some common
metals, e.g. copper ( I I ) , iron ( I I I ) , lead, nickel, cobalt, cadmium, zinc,
mercury ( I I ) , bismuth, aluminium, chromium ( I I I ) /67, 68/. Among the
rare earths, scandium has been separated from the lanthanides, zircon-
ium and titanium ( I V ) /69/. The extraction o f thorium and its separa-
tion f r o m the lanthanides has also been reported /41/. Similarly, the
extraction o f tungsten ( V I ) and zirconium has been studied /70, 71/.
A n interesting feature in the extraction of metal ions fronl acid medium
is the wide variation o f the acid concentrations at which different ions
exhibit highest extraction efficiency, e.g., the extractibility o f some
metals such as tin ( I V ) , tantalum and vanadium ( V ) increases with the
acidity o f hydrochloric acid up to 11M, using PBHA in chloroform as
the extractant. Further, the acid extractability o f various chelates o f
hydroxamic acids depends upon the nature o f the reagent, e.g. the
hydroxamic acids with aromatic substituents favour an organic solvent
122/.

Spectrophotometric Determination of Vanadium

The first used and still most popular compound for the spectro-
photometric determination o f vanadium ( V ) is N-phenylbenzohydrox-
amic acid ( P B H A ) . Shome had reported in 1951 that PBHA formed a
mahogany red complex with vanadium in 1:1 ethanol solution bettveen
pH 1.8 and 2.8 /72/. Later Priyadarshini and Tandon /73/ and Ryan /2/
independently developed a method for extraction and spectrophoto-

14
metric determination of vanadium from hydrochloric acid medium
(above 2M) in ethanol-free chloroform. However, in these methods, Zr,
Ti, Mo and W interfere in the determination of vanadium. Several other
hydroxamic acids such as N-phenylcinamo-/74/,N-p-tolyl-2-furo- /75/,
N-m-tolyl-o-methoxybenzo- /76/, and others /77,78/ have been reported
for vanadium /79-85/. Bass and Yoe /86/ proposed 2-naphthohydrox-
amic acid as a superior reagent for vanadium which gives in methanol
an intense red-orange colour with vanadium. Later Agrawal /87/ repor-
ted N-phenyl-2-naphthohydroxamic acid as a selective and sensitive
reagent for vanadium. Shendrikar /66/ has discussed in his review paper
the use of hydroxamic acid for the determination of vanadium. N-
benzoyl-N-p-chlorophenylhydroxylamine was reported as a sensitive
reagent for determination of vanadium and it can tolerate the presence
of titanium and zirconium, but not molybdenum and tungsten /88/.
Recently Agrawal /89/ reported N-m-tolyl-m-nitrobenzohydroxamic
acid for the determination of vanadium in the presence of Ti, Zr, Mo,
W and other metals. Many workers applied these reagents for the
determination of vanadium (V) in steel /90/, alloys /91/, ores /2, 73/,
blood /92/, urine /91/ and plant products and other complex materials
/91, 93/. A detailed review of several hydroxamic acids for the deter-
mination of vanadium is given in Table II and for other metal ions in
Table III.

General Procedure
Transfer an aliquot of vanadium solution containing 2-10 ppm of
vanadium to a 150 ml separatory funnel and add potassium permanga-
nate solution (0.05 M) dropwise until a faint pink colour persists in the
solution to ensure complete oxidation of vanadium to the pentavalent
state. Adjust the acidity to between 4 and 6 Μ with concentrated
hydrochloric acid and distilled water to a final volume of 25 ml and
then add 10 ml 0.1% W/v PBHA in ethanol-free chloroform. Shake the
contents vigorously for 5-10 minutes and allow the phases to separate.
Dry the chloroform extract over anhydrous sodium sulphate and trans-
fer it to a 25 mj volumetric flask. Repeat the extraction twice with 5 ml
of reagent solution to ensure the complete recovery of vanadium. Dilute
the extracts to 25 ml with chloroform and measure the absorbance at
530 nm against the reagent blank. The molar absorptivity is 45601 mol"1
cm"1 and the Sandell sensitivity index is 0.11 μ% of V/cm 2 at 530 nm.
Notes (1) 0.1% W/v PBHA solution has practically no absorbance at
530 nm; it can be replaced by pure chloroform.

15
 T A B L E II

Extraction and Spectrophotometry Determination of Vanadium

Hydroxamic Acids Acidity Solvent Colour Xmax e Ref

nm

N - Phenylbenzo- 6 M HCl CHCIJ V 520 4 6 5 0 73

N - Phenyl-O-methylbenzo- 6 M HCl CHCI3 BV 540 4 6 8 0 84
N - Pheny 1 - m - methy Ibenzo- 6 M HCl CHCIj BV 530 5150 85
N - Phenyl-p-methylbenzo- 6 M HCl CHCI3 BV 535 4800 84
N - Phenyl-o-methoxybenzo- 6 M HCl CHCI3 BV 530 4 2 0 0 81
N - Pheny 1 - p - methoxy benzo - 6 M HCl CHCI3 BV 535 5900 85
N - Pheny l - p - f luorobenzo- 6 M HCl CHCI3 V 525 4400 8 5
N -•Phenyl-o-chlorobenzo- 6 M HCl CHCI3 V 525 4 3 0 0 84
N - Pheny 1 - p-chlorobenzo - 6 M HCl CHCI3 V 525 4 5 0 0 84
N - Pheny l - o - b r o m o b e n z o - 6 M HCl CHCI3 BV 530 4450 85
N-Pheny l-m-bromobenzo- 6 M HCl CHCIJ V 525 4 3 0 0 84
N - Pheny 1 - p - bromobenzo - 6 M HCl CHCI3 V 525 4550 85
N - Phenyl-o-nitrobenzo- 6 M HCl CHCI3 V 525 4100 84
N - Phenyl-m-nitrobenzo- 6 M HCl CHCI3 RV 515 3600 84
N - Phenyl-p-nitrobenzo- 6 M HCl CHCI3 V 525 4 3 0 0 84
N - Pheny 1 - 3 , 5 - din i trobenzo - 6 M HCl CHCI3 RV 510 3300 84
N - Phenyl-1 - n a p h t o - 6 M HCl CHCIJ BV 540 4 4 5 0 84
N - Phenylcinnamo- 6 M HCl CHCI3 BV 540 6300 84,85
N - Phenyl-2-theno- 6 M HCl CHCI3 V 530 5450 84
N - Phenyl-2-furo- 6 M HCl CHCI3 V 530 4 6 5 0 84
N - Phenylphenylaceto- 6 M HCl CHCI3 RV 500 4 4 0 0 85
N -• Pheny Iphenoxyaceto- 6 M HCl CHCI3 RV 500 3 8 5 0 85
N - Phenyl-p-chloropheno-
xyaceto- 6 M HCl CHCI3 RV 500 3850 85
N - Phenyl-n-butyro- 6 M HCl CHCI3 RV 500 4500 85
N - Phenyl-n-valaro- 6 M HCl CHCI3 RV 505 4 0 5 0 81
N - Phenylcapro- 6 M HCl CHCI3 RV 510 4 0 2 0 81
N - Phenylcaprylo- 6 M HCl CHCI3 RV 510 4 0 0 0 81
N - Phenylcapri- 6 M HCl CHCI3 RV 500 4 1 5 0 81
N - Phenylmyristo- 6 M HCl CHCI3 RV 510 4 3 2 0 81
N - Phenylpalmito- 6 M HCl CHCI3 RV 500 4 4 0 0 85
N - Phenyl-lauro- 6 M HCl CHCI3 RV 500 4 4 0 0 85
N - Pheny I - 1 - naphthy laceto - 6 M HCl CHCI3 RV 510 4 3 0 0 81
N - Phenyl-2,4-dichloro-
phenoxyaceto- 6 M HCl CHCI3 Ry 505 3 0 5 0 81
N - Pheny lundecy leno - 6 M HCl CHCI3 RV 500 4150 81
N - O-Tolylbenzo- 6 M HCl CHCI3 V 5 1 0 ' 5 0 0 0 81
N - O-Tolyl-O-methylbenzo- 6 M HCl CHCI3 RV 510 4 5 0 0 81
N - O - T o l y l - m - m e t h y Iben z o - 6 M HCl CHCI3 V 510 5100 81

16
 T A B L E II (cont.)

Hydroxamic Acids Acidity Solvent Colour Xmax e Ref

nm

N - O-Tolyl-p-methylbenzo- 6M HCl CHCI3 V 510 5500 81

N - O-Tolyl-o-methoxylemo- 6M HCl CHCI3 BV 520 5000 81
N - O-Tolyl-o-chlorobenzo- 6M HCl C H CI 3 BV 505 3800 81
N - O-Tolyl-p-chlorobenzo- 6M HCl CHCIj V 505 5200 81
N - O-Tolyl-o-iodobenzo- 6M HCl CHCI3 V 510 4750 81
N - O-Tolylphenoxyaceto- 6M HCl CHCI3 RV 495 4230 81
N - O-Tolylphenylaceto 6M HCl CHCI3 RV 510 3900 81
N - m-Tolylbenzo- 6M HCl CHCI3 BV 525 4850 81
N - m-Tolyl-o-methylbenzo- 6M HCl CHCI3 V 515 4300 81
N - m-Tolyl-m-methylbenzo- 6M HCl CHCI3 BV 520 4900 81
N - m- Tolyl-p-methylbenzo- 6M HCl CHCI3 BV 520 5350 81
N - m - T o l y 1 - o - methoxybenzo - 6M HCl CHCI3 BV 520 4900 81
N - m-Tolyl-o-methoxybenzo- 6M HCl CHCI3 BV 550 6500 76,95
N - m-Tolyl-p-methoxybenzo- 6M HCl CHCI3 BV 530 5750 81
N - m-Tolyl-o-chlorobenzo- 6M HCl CHCI3 BV 530 4150 81
N - m-Tolyl-o-iodobenzo- 6M HCl CHCI3 BV 530 3800 81
N - m-Tolyl - m - n i trobenzo- 6M HCl CHCI3 V 540 3100 89
N - m-Tolyl-capri- 6M HCl CHCI3 RV 510 4450 81
N - p-Tolylbenzo- 6M HCl CHCI3 V 530 4700 84
N - p-Tolyl-o-methylbenzo- 6M HCl CHCI3 BV 530 4750 85
N - p -Tolyl - m - methy Ibenzo - 6M HCl CHCI3 BV 535 5250 85
N - p-Tolyl-p-methylbenzo- 6M HCl CHCI3 V 530 4900 85
N - p-Tolyl-o-methoxybenzo- 6M HCl CHCI3 BV 530 4700 81
N - p-Tolyl-p-methoxybenzo- 6M HCl CHCI3 BV 540 6100 85
N - p-Tolyl-p-fluorobenzo- 6M HCl CHCI3 V 530 4500 85
N - p-Tolyl-o-chlorobenzo- 6M HCl CHCI3 BV 530 4500 85
N - p-Tolyl-p-chlorobenzo- 6M HCl CHCI3 V 528 4600 84
N - p-Tolyl-o-bromobenzo- 6M HCl CHCI3 V 535 4500 85
N - p-Tolyl-m-bromobenzo- 6M HCl CHCI3 V 530 4450 85
N - p-Tolyl-p-bromobenzo- 6M HCl CHCI3 BV 530 4650 85
N - p-Tolyl-o-iodobenzo- 6M HCl CHCI3 BV 535 4400 85
N - p-Tolyl-m-nitrobenzo- 6M HCl CHCI3 RV 515 4700 81
N - p-Tolyl-p-nitrobenzo- 6M HCl CHCI3 V 530 4500 84
N - o-Tolyl-1 -naphtho- 6M HCl CHCI3 BV 545 4650 84
N - p-Tolylcinnamo- 6M HCl CHCI3 BV 555 6500 84
N - p-Tolyl-2-theno- 6M HCl CHCI3 V 530 5740 84
N- p-Tolyl-2-furo- 6M HCl CHCI3 V 532 4900 84
N- p-Tolyl-2-furo- 6M HCl CHCI3 V 540 3000 75
N - p - T o l y I - pheny laceto - 6M HCl CHCI3 RV 505 4500 85
N -•p-Tolyl-phenoxyaceto- 6M HCl CHCI3 RV 510 3950 81
N - p-Tolyl-2,4-dichlorophe-
noxyaceto- 6M HCl CHCI3 RV 500 3250 81

17
 T A B L E II (cont.)

Hydroxamic Acids Acidity Solvent Colour Xmax 6 Ref

nm

N-p-Tolyl-n-butyro- 6 M HCl CHCIJ RV 505 4500 85

N-p-Tolyl-n-Valaro- 6M HCl CHCI3 RV 510 4350 81
N-p-Tolylcapro- 6M HCl CHCI3 RV 510 4350 81
N - ρ - T o l y Icapry lo - 6M HCl CHCIj RV 510 4200 81
N-p-Tolyl-capri- 6M HCl CHCI3 RV 510 4450 81
N-p-Tolylmyristo- 6M HCl CHCI3 RV 515 4300 81
N-p-Tolylundecyleno- 6M HCl CHCI3 RV 515 4500 81
N-p-Tolylbehero 6M HCl CHCI3 RV 510 4150 81
N - 1 -Naphthylbenzo- 6M HCl CHCI3 RV 515 4450 84
N - 1 - Naphthyl-o-methyl- 6M HCl CHCI3
benzo- 6M HCl CHCI3 BV 530 4700 81
N - 1 - N a p h t h y l - p - m e t h y l b e n z o -- 6 M HCl CHCI3 V 510 4900 81
N - 1 -Naphthyl-o-methoxy-
benzo- 6M HCl CHCI3 BV 525 4700 81
N - 1 -Naphthyl-p-methoxy-
benzo- 6 M HCl CHCI3 BV 520 5400 81
N - 1 -Naphthyl-p-chloro-
benzo- 6M HCl CHCI3 BV 510 4350 81
N - 1 -Naphthyl-p-nitrobenzo- 6M HCl CHCI3 RV 505 4500 81
N - 1 -Naphthylphenylaceto- 6M HCl CHCI3 RV 505 4000 81
N-1-Naphthyl-n-valaro- 6M HCl CHCI3 RV 510 4350 81
N - 1 -Naphthylcapro- 6M HC1 CHCI3 RV 495 4250
N - 1 -Naphthylcapri- 6M HCl CHCI3 RV 495 4150 81
N - 1 -Naphthylmyristo- 6M HCl CHCI3 RV 500 3850 81
N - 1 -Naphthyl-Iauro- 6M HCl CHCI3 RV 500 3800 81
N-O-Tolyl-O-fluorobenzo- 6M HCl CHCI3 V 525 4400 97
N-O-Tolyl-p-fluorobenzo- 6M HCl CHCk 3 V 525 4500 97
N-O-Tolyl-o-bromobenzo- 6M HCl CHCI3 V 530 4500 97
N - O - T o l y l - m-bromobenzo- 6M HCl CHCI3 V 525 4400 97
N-O-Tolyl-p-bromobenzo- 6M HCl CHCI3 V 530 4600 97
N-O-Tolyl-p-iodobenzo- 6M HCl CHCI3 V 530 4100 97
N-O-Tolyl-o-nitrobenzo- 6M HCl CHCI3 V 510 4300 97
N-O-Tolyl-m-nitrobenzo- 6M HCl CHCI3 RV 515 4200 97
N-O-Tolyl-p-nitrobenzo- 6M HCl CHCI3 RV 515 4400 97
N-0-Tolyl-3,5-dinitrobenzo- 6M HCl CHCI3 RV 500 3900 97
N - Phenyl - 2 - naphtho 6M HCl CHCI3' V 545 7100 87
N-p-Tolyl-palmito- 6M HCl CHCI3 RV 505 4500 79
N-Phenyl-2-furanacrylo- 6M HCl CHCI3 - 560 6200 77
N - ρ - T o l y 1 - furanacry lo - 6M HCl CHCI3 - 570 6400 77

pH 1.0 H2O-
capro-
Me 2 CO(4:6) orange 460 ~ 96

V = violet, B V = bluish violet, R V = reddish violet

18
 T A B L E II (cont.)

Hydroxamic acids Acidity Solvent Colour Xmax 6 Ref

nm

Ν -Phenyl -3-Styrylachy lo- 4 M HCl CHCIj BV 555 7500 78

N-Phenyl-p-methoxy-
cinnamo- 4 M HCl CHCIj BV 570 7500 78
N -m-Tolyl-p-methoxy -
cinnamo- 4 M HCl CHCI3 BV 570 7500 78
N-p-Tolyl-p-methoxy-
cinnamo- 4 M HCl CHCIj BV 570 7500 78
N-p-Chlorophenyl-p-
methox y c i n n a m o - 4 M HCl CHCIj BV 570 7400 78
N - m - T o l y 1 - 3 , 4 - m e t h y lene-
dioxycinnamo- 4 M HCl CHCI3 BV 570 7500 78
N-p-Tolyl-3,4-methylene-
dioxycinnamo- 4 M HCl CHCIj BV 570 7500 78
N-p-Chlorophenyl-3,4-
methylenedioxycinnamo- 4 M HCl CHCI3 BV 570 740p 78
N-O-Tolylcinnamo- 4 M HCl CHCI3 BV 530 6300 78
N - m - T o l y lei n n a m o - 4 M HCl CHCI3 BV 540 6200 78
N-p-Chlorophenylcinnamo- 4 M HCl CHCI3 BV 535 6300 78
N-m--Tolyl-2-furanacrylo- 4 M HCl CHCI3 BV 570 6300 78
N-p-Chlorophenyl-2-
furanacrylo- 4 M HCl CHCI3 BV 570 6100 78
N-Phenylsorbo- 4 M HCl CHCI3 BV 550 5500 78
N-m-Tolylsorbo- 4 M HCl CHCI3 BV 550 5500 78
N-p-Tolylsorbo- 4 M HCl CHCI3 B V 555 5500 78
N-p-chlorophenylsorbo- 4 M HCl CHCI3 B V 550 5100 78
N-Phenylcrotone- 4 M HCl CHCI3 V 535 4400 78
N-p-Tolylcrotono- 4 M HCl CHCI3 V 540 4800 78
N-p-Chlorophenylcrotono- 4 M HCl CHCI 3 V 530 4400 78

(2) Ethanol-free chloroform is obtained by washing commercial

chloroform 3-4 times with about half its volume o f water,
drying over fused calcium chloride and finally distilling it.

Spec tropho tome trie Determination of Titanium /98/

To 5 ml of the titanium solution (1.041 χ 10" 3 M), 15-20 ml concen-
trated HCl and 5 ml of 0.1% chloroform solution of the reagent (N-
phenyl-m-methylbenzohydroxamic acid) are added. The mixture is
shaken for 10-15 minutes and the chloroform layer allowed to separate.
The yellow extract thus obtained is dried over anhydrous sodium sul-

19
 T A B L E III

Extraction and Spectrophotometric Determination of Metals with

Hydroxamic Acids

Hydroxamic Acids pH/acidity Solvent Colour Xmax e Ref

nm

Metal A : Titanium (IV)

Benzo- 5 - 8 M HCl Hexanol Yellow 370 2400 49,
100
N -Phenyl -m-methylbenzo- conc. HCl CHCI3 Yellow 410 5700 9 8

Metal B: Molybdenum (VI)

Benzo- 2-3 Hexanol Yellow 370 101
Greenish
Benzo- 2-3 Hexanol Yellow 370 2.2 102
Green χ 10 3

Metal C: Cerium (IV)

N-p-Tolylbenzo- 8.5 CHCI3 Red 465 4600 103
N-m-Tolyl-m-nitrobenzo- 8.0-9.8 CHCI 3 Red 465 4000 104
N-p-Tolyl-2-furo- 8.5-9.5 CHCIj Red 465 105
Brown

Metal D: Uranium (VI)

N-phenylbenzo- 4 CHCI3 Blood- 510 - 106
Red
N-Phenyl-2-naphtho- 4-4.5 CHCI3 Orange- 5 1 5 - 107
Red
N-m-Tolyl-o-methoxybenzo- 5.3-5.5 CHCI, 0 range - 5 1 0 - 108
Red
N-p-Tolylbenzo- 4.3 CHCI3 Red 515 - 109
N-m-Tolyl-m-nitrobenzo- 4.5 CHCI, Red 510 - 110
Benzo- 6.2 Hexanol -

Metal E: Iron (III)

p-Nitrobenzo- 4.8-5.0 Ethyl Yellow 430 - • 111
Acetate

phate to remove moisture and transferred to a 25 ml volumetric flask.

To ensure the complete recovery of titanium, the aqueous layer should
be extracted twice with 5 ml of reagent solution and sodium sulphate
then washed with 2 ml (x3) of chloroform to remove the last traces of
yellow colour. Finally, the extracts are diluted to the mark. The absorb-
ance of the yellow extract is measured at 410 nm, against a reagent
blank.

20
 Beer's law is obeyed over the range of 0.5-10 ppm of titanium. The
molar absorptivity of the yellow titanium-N-phenyl-m-methylbenzo-
hydroxamate complex at 410 nm is 5.7 χ 10 3 1 mol"1 cm" 1 .

Spectropho tome trie Determination of Molybdenum with Benzohydrox-

amic Acid /102/
Place 2 ml of molybdenum solution in a separating funnel and add
8 ml of conc. hydrochloric acid. 10 ml of 0.1 Μ solution o f b e n z o -
hydroxamic acid in water are added and a yellow-greenish coloured
complex is formed. 10 ml of 1-hexanol are added and the contents are
shaken for 5 minutes. The phases are allowed to separate, and the
organic phase is carefully transferred to a 25 ml flask after drying over
anhydrous sodium sulphate. Extraction should be repeated twice to
ensure the complete recovery of molybdenum. Finally the extracts are
diluted to 25 ml with hexanol. The absorbance of the yellow-greenish
coloured complex is measured at 370 nm against a reagent blank. The
amount of molybdenum is then computed from the calibration curve
(0.5-40 ppm). The molar absorptivity at 370 nm is 2.2 χ 10 3 1 mof'cm" 1 .

Spectrophotometric Determination of Cerium with N-phenyl-2-naphtho-

hydroxamic Acid /105a, 106/
10 ml of a chloroform solution of the reagent are added to 10 ml
of cerium (IV) solution in a 100 ml separatory funnel. The pH of the
solution is adjusted to pH = 8.5 by adding 10 ml of buffer solution. The
contents are shaken for 10 minutes and the organic phase is allowed to
separate, dried over anhydrous sodium sulphate and transferred to a
25 ml volumetric flask. To ensure complete recovery of the cerium, the
aqueous phase is extracted twice with 3 ml of reagent solution and the
sodium sulphate is washed with 2 (x3) ml of chloroform. Finally the
extract is diluted to the mark with chloroform. The spectrum is recor-
ded and the absorbance measured at 470 nm against a reagent blank
using 10 mm cells. The molar absorptivity is 5.5 χ 10 3 1 mol" 1 cm" 1 .

Spectrophotometric Determination of Uranium (VI) with N-phenyl-2-

naphthohydroxamic Acid /107/
An aliquot of uranium solution (2.5 ml of 2.49 χ 10"3M) is taken
and its pH adjusted to 4 with 0.01 Μ KOH in a total volume of 10 ml.
10 ml of 0.1 Μ chloroform solution of the reagent are added and the
contents shaken in a 100 ml separatory funnel for 10 minutes. The
phases are allowed to settle and the orange-red organic layer separated

21
and carefully transferred to a 25 ml volumetric flask after drying over
anhydrous sodium sulphate. The extraction should be repeated twice to
ensure complete recovery of uranium. Finally the extracts are diluted
to 25 ml with chloroform. The absorbance of the orange-red coloured
complex is measured at 515 nm against a reagent blank.

Spec tropho tome trie Determination of Iron (III) with p-Nitrobenzo-

hydroxamic Acid /111/
2 ml of iron solution and 10 ml of the reagent solutions are added to
a 50 ml beaker. This is diluted to 25 ml and the pH adjusted to 4.8-5.0
using 0.01 Μ ammonium hydroxide and 0.01 Μ sulphuric acid. The
chelate solution formed is transferred to a 100 ml separatory funnel
and 10 ml of ethyl acetate are added. The contents are shaken for 5-10
minutes and the organic layer allowed to separate. The yellowish orange
extract obtained is taken in an Erlenmeyer flask containing 1 g of an-
hydrous sodium sulphate (B.D.H. Analar). The dried organic phase is
then transferred to a 25 ml volumetric flask. To ensure complete re-
covery of iron, the above procedure is repeated with 3 ml of the reagent.
The combined extracts are made up to the mark. The spectra are
scanned and the absorbance measured at 430 nm against an ethyl
acetate blank. The results should be accurate to within ±0.5%.

Spectrophotometric Determination of Niobium with N-phenyl-benzo-

hydroxamic Acid /112/
For samples which do not require fuming with H 2 S 0 4 pipette an
aliquot containing 2-20 ßg of niobium into a 60 ml separatory funnel.
Add 20 ml of 12 Μ HCl, 1 ml of SnCl 2 solution, and mix thoroughly.
From this point on, the specified times should be followed fairly closely
as large deviations may lead to erratic results. Add 1 ml of 1% PBHA,
mix thoroughly, and allow to stand for 1 minute. Extract the Nb-PBHA
complex into 10 ml of toluene by shaking for 1 minute. Allow the
phases to separate completely; drain off and discard the aqueous phase.
Add 20 ml of 4 Μ HCl and 5 ml of 25% NH„SCN solution and shake
for 1 minute. As soon as the toluene phase is clear, transfer a portion
or drain through cotton into a 1 cm cell and measure the absorbance at
365 nm. The colour measurement must be made within 1 hour of
adding the NH 4 SCN solution. Run blanks and standards with the
sample as described above.

22
Non-Aqueous Titrations of Hydroxamic Acids /113-115/
Hydroxamic acids have been titrated visually against 0.1 Μ tetra-
butyl ammonium hydroxide in a non-aqueous medium with O-nitro-
aniline as the indicator. The titrations have also been carried out poten-
tiometrically. These data are summarised in Table IV.

T A B L E IV

Non-Aqueous Titration of Hydroxamic Acids

S.N. Hydroxamic Acid Solvent Colour Molecular wt. Ref

change Formal Calculated

1 Benzo- DMF Y - R 135.05 137.17 113

MeOH PY - R
2 p-Methylbenzo- DMF Y-OR 151.00 151.17 113
MeOH PY - R
3 p-Methoxybenzo- DMF Y - RD 166.98 167.17 113
MeOH PY - R
4 p-Fluorobenzo- DMF Y - PO 155.24 155.13 113
MeOH PY - R
5 p-Chlorobenzo- DMF Y - 0 171.20 171.62 113
MeOH Y-OR
6 p-Bromobenzo- DMF Y-OR 215.96 216.05 113
MeOH Y-OR
7 p - lodobenzo- DMF Y-OR 263.95 263.64 113
MeOH Y-OR
8 p-Nitrobenzo- DMF Pt 181.96 182.19 113
MeOH Pt
9 p-Aminobenzo- DMF Pt 152.36 152.18 113
MeOH Pt
10 p-Cyanobenzo- DMF Pt 162.51 162.16 113
MeOH Pt

DMF = Dimethyl formamide; MeOH = Methanol; Pt = Potentio metrically.

Y = Yellow; R = Red; OR = Orange Red; RD = Reddish; PO = Pink Orange;
Ο = Orange; PY = Pale Yellow.

A weighed amount of hydroxamic acid is transferred into a 20 ml

titration vessel with C-10 joints for the burette and nitrogen inlets.
10 ml of dimethylformamide are added and the mixture stirred by
means of a magnetic stirrer. Two drops of a standard solution of
O-nitroaniline are added and the titration carried out again in 0.1 Μ

23
tetrabutyl ammonium hydroxide in an atmosphere of nitrogen. These
acids are similarly titrated potentiom etrically using platinum electrodes,
trodes.

Detection of Hydroxamic Acids /116/

Mix one drop of vanadium solution with two drops of the concen-
trated hydrochloric acid, with warming if necessary, in a microscale
test tube. Cool the mixture, add one drop of solution of the sample in
chloroform and shake it vigorously. If a hydroxamic acid is present a
violet colour that is extracted into the organic phase develops in a few
seconds. The coloured complex is stable for several days.

24
 REFERENCES

1. YALE H.L. Chem. Rev. 33: 209 (1944).

2. RYAN D.E.Analyst 85: 569 (1960).
3. GUPTA HJC.L. and SOGANI N.C. J. Indian Chem. Soc. 37: 769 (1960);
40: 15 (1963).
4. PRIYADARSHINI U.and TANDON S.G./. Chem. Eng. Data 12:143 (1967).
5. TANDON S.G. and BHATTACHARYYA S.C. J. Chem. Eng. Data 7: 553
(1962).
6. BHURA D.O. and TANDON S.G. J. Chem. Eng. Data 16: 106 (1971); 14:
278(1968).
7. AGRAWAL D.R. and TANDON S.G., /.'Chem. Eng. Data, 17: 257 (1972).
8. GUPTA VJC. and TANDON S.G. J. Indian Chem. Soc. 46: 831 (1962).
9. AGRAWAL YJC. and TANDON S.G. J. Chem. Eng. Data 16: 371 (1971);
16: 495 (1971);/. Indian Chem. Soc. 48: 397 (1971).
10. AGRAWAL Y.K. J. Chem. Eng. Data 22: 70 (1977).
11. AGRAWAL Y.K. Russ. Chem. Rev. In Press.
12. HADZID. and PREVORSEK D. Spectrochim. Acta 10: 38 (1957).
13. PILIPENKO A.T., SHAP Ε .A. and SHEVCHENKO L. Russ. J. Inorg. Chem.
12: 237 (1967).
14. EXNER O. and HOLUBEK J. Collection. Czech. Chem. Commun. 30: 940
(1966).
15. AGRAWAL Y.K. and TANDON S.G. J. Indian Chem. Soc. 49: 911 (1972).
16. BAUMGARTEN H.E., STAKLIS A. and MILLER E.M. J. Org. Chem. 30:
1203 (1965).
17. FARHA F. M.S. Thesis, Wichita State Univ., Kansas (1967).
18. MOSHIER R.W. and SCHWARBERG J.E.Anal. Chem., 29: 946 (1957).
19. ELLEFSEN P.R., GÖRDEN L., BELCHER R. and JACKSON W.G. Talanta
10: 701 (1963).
20. BELCHER R., WILSON C.L. and WEST T.S., New Methods of Analytical
Chemistry, 2nd Ed., Chapman and Hall Ltd., London (1964).
21. SHOME S.C.Analyst 75: 27 (1950).
22. MAJUMDAR A.K., N-Benzoylphenylhydroxylamine and its Analogues,
Pergamon Press, London (1971).
23. BHURA D.C. Technical News Service Sarabhai M. Chemicals, Baroda, India
5: (3) (1973); 5: (4) (1973).
24. KAPOOR H.L., AGRAWAL YJC. and VERMA P.C. Talanta 22: 193 (1975).
24a AGRAWAL Y.K.; Talanta, 20: 1213 (1973).
25. AGRAWAL Y.K. and KAPOOR H.L. Analusis 3 (8): 424 (1975).
26. AGRAWAL Y.K. and KAPOOR H.L. Analusis 5 (2): 62 (1977).
26a. SINHA S X . and SHOME S.C. Anal. Chim. Acta 21: 459 (1959).
27. DAS H.R. and SHOME S.C .Anal Chim. Acta 27: 545 (1962).
28. ALIMARIN Ii>. and HAMID S.A. Zhur. Anal. Khim. 18: 268 (1964).
29. DAS D. and SHOME S.C. Anal. Chim. Acta 35: 345 (1966).
30. DAS B. and SHO^E S.C. Anal. Chim. Acta 32: 52 (1965).
31. GARDWELL Τ J . and MAGEE R.J. Microchem. J. 13:467(1968).
32. SINHA S.K. and SHOME S.C. Anal. Chim. Acta 24: 33 (1961).
33. SINHA S.K. and SHOME S.C. Cur. Sei. 26: 249 (1959).
34. MAJUMDAR A.K. and MUKHERJEE A.K. Ζ. Anal. Chim. 189: 339 (1962).
35. LANGMYHR F.J. and HONGALO Τ .Anal. Chim. Acta 22: 301 (1960).
36. MAJUMDAR A.K. and MUKHERJEE A.K. Anal. Chim. Acta 19: 23 (1958).
37. MAJUMDAR A.K. and MUKHERJEE A.K. Anal. Chim. Acta 21: 245 (1959).
38. MOSHIER R.N. and SCHWARBERG J £ . , WADC Tech. Report, 56-300
(1956).
39. ALIMARIN I.P. and YUNG-SCHAING T. Zavodsk. Lab. 25: 1435 (1959);
Talanta 10: 701 (1963).
40. RYAN D.E. and LUTWICK G.D. Can. J. Chem. 31: 9 (1953).
41. ALIMARIN I.P. and YUNG-SCHAING T. Vestn. Mosk. Uriv. Ser. II Khim.
15: 53 (1960); Cf. C.A. 55: 2449(1961).
42. DAS B. and SHOME S.C. Anal. Chim. Acta 33: 462 (1965).
43. KAIMAL V.R.M. and SHOME S.C. Anal. Chim. Acta 29: 286 (1963).
44. KA1MAL V.R.M. and SHOME S.C. Anal. Chim. Acta 27: 298 (1962).
45. SCHWARBERG J.E. and MOSHIER RW.Anal. Chim. Acta 34: 525 (1965).
46. DAS J. and SHOME S.C .Anal. Chim. Acta 27: 58 (1962).
47. KAIMAL V.R.M. and SHOME S.C Anal. Chim. Acta 31: 268 (1964).
48. RYAN D.E. Can. J. Chem. 38: 2488 (1960).
49. MAJUMDAR A.K. and PAL B.K. J. Ind. Chem. Soc. 42: 43 (1965).
50. CASSIDY P.M. and RYAN D.E.,4na/. Chim. Acta 41: 319 (1968).
51. MAJUMDAR A.K. and MUKHERJEE A.K. Anal. Chim. Acta 22: 514
(1960).
52. GOSH N.N. and BHATTACHARYYA A. J. Ind. Chem. Soc. 44: 972 (1967).
53. AGRAWAL Y X „ SHASHIMOHAN A.L. and RAO V. Talanta 20: 626
(1974).
54. VERMA P.C., AGRAWAL Y.K. and KHADIKAR P.V. J. Indian Chem. Soc.
52: 176 (1975).
55. VERMA P.C., KHADIKAR P.V. and AGRAWAL Y.K. Indian J. Chem. 14A:
637 (1976).
56. SAVARIEV C.P. and JOSHEPH J. Anal. Chim. Acta 47: 347 (1969).
57. PODDAR S.N., SEN GUPTA N.R. and ADHIYA J.N. Sei. Cult. 29: 258
(1963).
58. MAJUMDAR A.K. and PAL B.K. Z. Anal. Chem. 184: 115 (1961).
59. MAJUMDAR A.K. and PAL B.K.Anal. Chim. Acta 27: 356 (1962).
60. ABRAHAM I.D., ABRAHAM J. and RYAN D.E. Anal. Chim. Acta 48: 93
(1969).
61. AGRAWAL Y.K.Indian J. Chem. 14A: 1024 (1976).
62. LAHARI S.J.Indian Chem. Soc. 51: 841-912 (1974).
63. SINHA S.K. and SHOME S.C .Anal. Chim. Acta 21: 415 (1959).
64. BAG S.P. and LAHIRI S. Cur. Sei. 43: 307 (1974).
65. DRYSSEN D.Acta Chem. Scand. 10: 353 (1956).
66. SHENDRIKAR A.D. Talanta 16: 51 (1969).
67. CHWASTOWISKA J. and MINCIZEVOSKII J. Chem. Anal. 8: 157 (1963).
68. CHWASTOWISKA J. and MINCIZEVOSKII J. Chem. Anal. 9: 791 (1964).
69. ALIMARIN I.P. and YUNG-SCHAING T. Talanta 8: 317 (1961).
70. CHE MING NEE, CHUNG FENCHU and SHUCHUAN, Liang Hua-Hsuch
Pao 29: 247 (1963); Cf. C.A. 62: 5872 (1965).

26
 71. CHE MING NEE, CHUNG FENCHU and SHUCHUAN, Liang Hua-Hsuch
Pao 30: 296 (1964); Cf. C.A. 61: 11309 (1964).
72. SHOME S.C. Anal. Chem. 23: 1186 (1951).
73. PRIYADARSHINI U. and TANDON S.G. Chem. & Ind. (London) 931
(1960); Anal. Chem. 33: 569 (1960).
74. PRIYADARSHINI U. and TANDON S.G.Analyst 86: 379 (1961).
75. AGRA WAL Y.K .Anal. Letters 7: 729 (1974).
76. AGRAWAL Y.K., CHATTOPADHAYAYA M.C., ABBASI S.A. and
BODAS M.C. Sep. Sei. 8: 613 (1973).
77. BHURA D.C. and TANDON S.G. Indian J. Chem. 8: 1036 (1970).
78. BHURA D.C. and TANDON S.G. Anal. Chim. Acta 53: 379 (1971).
79. TANDON U. and TANDON S.G. J. Indian Chem. Soc. 46: 983 (1969).
80. TANDON S.G. and BHATTACHARYYA S.C. Anal. Chem. 33: 1267
(1961).
81. GUPTA V.K. and TANDON S.G. Anal. Chim. Acta 66: 39 (1973).
82. MARU P.C. and KHADIKAR V.V.Anal. Letters 9: 147 (1976).
83. ABBASI S.A. Anal. Chem. 48: 714 (1976).
84. TANDON S.G. and BHATTACHARYYA S.C. J. Indian Chem. Soc. 47:
583(1970).
85. TANDON U. and TANDON S.G. J. Indian Chem. Soc. 46: 983 (1969).
86. BASS V.C. and YOE LH. Anal. Chim. Acta 35: 337 (1967).
87. AGRAWAL Y.K.Anal. Chem. 47: 940 (1975).
88. MAJUMDAR A.K. and DAS G. J. Indian Chem. Soc. 42: 189 (1965).
89. AGRAWAL Y.K. / . Indian Chem. Soc. 54: 454 (1977).
90. DE POOL D.H. and CADAVIECO R.D. Anal. Chem. 36: 93R (1964).
91. PRIYADARSHINI U. Ph.D. Thesis, University of Jabalpur, Jabalpur(1965).
92. AGRAWAL Y.K. and SANT M.S. Bio-Inorganic Chem. 9: 369 (1978).
93. AGRAWAL Y.K., RAJ K.P.S. and SANT M.S.Microchem. J. in press.
94. STARY J. Solvent Extraction of Metal Chelates, Pergamon Press, Oxford,
1964, p. 123-127.
95. AGRAWAL Y.K. Anal. Letters 5 : 8 6 3 (1972).
96. POPOVA V.F. and MARKMAN A.L. Uzbek.sk Khim. Zh. 10: 18 (1966).
97. AGRAWAL Y.K. J. Indian. Chem. Soc. communicated.
98. AGRAWAL Y.K.Ann. Chim. 67: 491 (1977).
99. AGRAWAL Y.K., PATKE S., SHARMA T.P., VERMA P.C. and MARU
P.C. Z. Anal. Chem. 280: 30 (1976).
100. AGRAWAL Y.K. Chemical Era 11: 21 (1975).
101. AGRAWAL Y.K., MARU P.C., SHARMA T.P., PATKE S. and VERMA
P.C. Z. Anal. Chem. 276: 300 (1975).
102. AGRAWAL Y.K. J. Indian Chem. 54: 451 (1977).
103. AGRAWAL Υ.K. Mikrochim. Acta 595 (1976).
104. AGRAWAL Y.K. and KAPORR H.L.Ann. Chim. 66: 117 (1976).
105. AGRAWAL Y.K. Chem. Anal. 22: 215 (1977).
105a. AGRAWAL Y.K.Chem. Analtz. communicated.
106. SHUKLA J.P., AGRAWAL Y.K. and BHATT K. Sep. Sei. 8: 387 (1973).
107. AGRAWAL Y.K. Sep. Sei. 8: 709 (1973).
108. AGRAWAL Y.K. Sep. Sei. Id: 167 (1975).

27
 109. AGRAWAL Υ.Κ. Anal. Letters 8: 257 (1975).
110. AGRAWAL Υ.Κ./4/ιη. Chim. 66: 371 (1976).
111. AGRAWAL Y.K., MUDALIAR Α., SHASHIMOGAN A.L. and RAO V.
J. Indian Chem. Soc. 53: 617 (1976).
112. VILLARREAL R. and BARKER S.A. Anal. Chem. 41: 611 (1969).
113. AGRAWAL Y.K.Analyst 9 7 : 5 7 8 (1972).
114. AGRAWAL Y.K.Analyst, communicated.
115. JAISWAL R.P. J. Indian Chem. Soc. 47: 755 (1970).
116. AGRAWAL Y.K.Analyst 98: 147 (1973).

28