Indian Journal of Chemical Technology

Vol. 8, May 200 1, pp. 200-203

Spectrophotometric determination of manganese(II) by picolinaldehyde

nicotinoy!hydrazone
R B Pawar, S B Padgaonkar & A D Sawant*
Inorganic Chemistry Division, The Institute of Science, 15, Madam Cama Road, Mumbai 400 032, lr d ia
Received 07 December 1999; accepted 18 Janu(//y 2001

Manganese (II) forms a ye llow coloured complex with a reagent picolinaldehyde nicotinoylhydrazone (PANH), which
can be quantitative ly ex tracted into ch loroform in the pH ran ge 8.7-10.5. Beer's law was obeyed over the concentration
ran ge of 0.02-1 .5 ppm with absorption maxima at 385 nm. The molar absorptivity and Sande ll 's sensitivity of the extracted
spec ies was found to be 4.606 x 104 L mol- 1 cm- 1 and 1.19 ng cm- 2 respectively. The nature of the complex was determined
by different methods and it was found to be I :2 (Meta l: Ligand ). Interference due to diverse ions has been studied. The
proposed method is simple, rapid, accurate, sensitive and has been applied for separation and determination of Mn(ll ) in
synt heti c mixtures and real samples.

Manganese as micronutrient has a very important by dissolving 4.503 g of MnCh.4H 20 in 250 mL of

biological significance. Industrially it has also a g reat distilled water with few drops of coned HCl and was
significance, especially in steel industry used as a standardised gravimetricall y 13 . The working solutions
hardenin g agent and as an additive to counter act the were prepared by appropriate dilutions. The reagent
14
effects of the sulphur in stee l and the major was synthesised by the reported method
percentage is consumed by steel industry.
Manufacturing of dry cells and alloys also consume Method
significant amount of manganese. Thus determination To an aliquot of soluti on containing 0.2-15 1--1-g of
of manganese in chemical and biological samples is Mn(IJ), 1 mL of 3.54 x 10- 3 M reagen t was added and
often required. the pH of solution was adjusted by 2 mL of buffer
Number of reagents had been reported ,_, 2 for the (HC l + NH 40H) of pH 9 and the total volume was
spectrophotometric determination of manganese, made 10 mL using distilled water. Prior to pH
however these methods suffer from the limitations adjustment, addition of reagent is necessary to prevent
such as longer extraction time3.7, lower sensitivity and manganese precipitation. The sol utio n mixture was
mo 1ar a bsorpt ·tvtty· I ·2 ·4 ·6 ·7·10- 17-, ·
requtres stan d'mg transfened into a separatory funne l and was
35689
time · · · · , and interference from large number of eq uilibrated for 30 s with 10 mL of ch loroform. The
ions'- 10· 1' usually associated with manganese. In the absorbance of yellow organic phase containing
present investigation, picolinaldehyde nicotinoyl- Mn(II)-PANH comp lex was measured
hydrazone (PANH) is used for the first time as an spectrophotometrically at 385 nm against reagent
analytical reagent for the extractive separation and blank.
spectrophotometric determination of manganese(II) at
trace levels. Determination of manganese(II) m synthetic
mixtures and real samples
Experimental Procedure The present method was applied in determination
of manganese (10 IJ.g) in various synt hetic mixtures
Apparatus and reagents
and metallurgical samples containing known amounts
The absorbance measurements were made on
Shimadzu 160 A UV- Vis spectrophotometer and of manganese. The results were found to be in good
GBC 932 AA, atomic absorption spectrophotometer. agreement (Table 1).
Aluminium drilling sample (0.12 g, Ita Lab) was
Eli co, model EQ-61 0, pH meter with combined g lass
electrode for the pH measurements. dissolved by heating with 15 mL coned HCl and 2 mL
The stock solution of manganese(II) was prepared HN0 3 and evaporated to nearly dryn ess . The residue
formed was extracted in 20 mL of distilled water and
*For correspondence finally dilution was made to known volume.
 PA WAR et at.: SPECTROPHOTOMETRIC DETERMINATION OF MANGANESE(Il) BY PICOLINALDEHYDE 201

·U., r -- - - - - - -- -- - - - - - - ,
Slope • 1.94 ~ 2 .0

~0.4

80 -0.6

0
c g -0.8
~u 60 ...J
e
j(
w
~ ·1
40

· 1.2

· 1.4 1------------~-----l
....
-4.2 ·3.9 -3.8 ·3.7 ·3.6
Log (PANH)

0 5 6 7 9 10 11 12 13
pH
Fig. 3-Log-log plot man ga nese(Il ) for the determinati on of
co mposition o f the co mpl ex
Fig.-Extracti on of manganese( II ) as a fun cti on o f pH
The extraction of manganese from all abo ve
0 .9 r -- - -- - -- - - - - -- - -----,
sample solution was carried out using 3.54 x I 0-l M
A
0.8 PANH with chloroform. Replicate analyses were
carried out and results obtained were compared with
0 .7 those obtained by AAS. They were found in good
agreement.
0 .6

0 .5
Results and Discussion
Extraction as a function of pH
0 .4 Manganese(II) from the pH range of 1.0-11.5 using
HCI to NH 4 0H medium was extracted with PANH
0 .3 with chloroform as solvent and the extraction was
found to be quantitative from 8.7-10.5 pH. Hence all
0.2
the extractions were carried out at pH 9.0 (Fig. 1).
0.1 B
Extraction as a function of PANH concentration
Manganese(II) was extracted with varying
oL_------------~~~~~~--~
3 40 3 50 360 3 70 3 80 390 400 410 4 20 4 30 440 450 460 470 480 490 500 concentration of PANH (4.42 x 10- 5 to 6.63 x 10-1 M).
Wavelength, nm It was observed that the extraction of I 0 J..tg of
manganese( II) was quantitative (99.63 %) with
Fig. 2-Absorpti on spectra o f man ga nese(II )-PA NH and PANH.
1.77 x 10-4 M PANH in 10 % ethano l. Excess of
Spec trum A: Mn(li )- PANH aga inst reage nt blank. Spec trum B:
PANH against chloroform reagent concentration did not show any effect on the
extraction and spectrophotometric determination of
Each of mild steel samples (0.5 & 0.512 g, Ita Lab) manganese(II) . Hence, a somewhat higher
was dissolved in 10 mL of aqua-regia and was concentration, 3.54 x 10-4 M of PANH was used for
evaporated nearl y to dryness and extracted with 10 further studies.
mL of 2M HN0 3 and diluted to known volume with
double distilled water. Absorption spectra
Fe-Mn powder sample (0.2 g, Ita Lab) was opened The absorption spectra of mangan ese(Il)-PANH
in I 0 mL of aqu a-regia and was evaporated nearly to complex in chloroform showed an absorption maxima
dryness and extracted with 10 mL of 2M HN0 3 and at 385 nm against reagent blank. At this wavelength
diluted to known volume with double distill ed water. the reagent did not show any significant absorbance.
202 INDIAN J. CHEM . TECHNOL., MAY 2001

Table I -Determinati o n of man ganese( II) in synthetic m ixtures and real samples

Synthetic mixtures Certified value Amount found * S.D. (%) C. Y . (%)

(%) (%)

M n( I 0). Ag( I 00), Fe( I 00) 99. 84 0.151 0.151

Mn( I 0), Cr(50), Pd(50) 99.86 0.1 8 1 0.1 8 1
Mn ( IO). Mg(IOO), Au(IOO) 99 .94 0.194 0.194
Mn(IO), Hg#(IOO), Cr(50) 99.90 0.2 0 .2
Mn ( I 0), Y ( 100), Pt( I00) 99.80 0.122 0 . 122

Real samples

Aluminium drilling s 0. 87 0. 85 0.002 0.263

(Ita Lab )
Mild stee l- I 1.15 1.14 0.002 0. 239
(It a Lab)
Mild stee l-2 0.74 0 .73 0.002 0. 375
(Ita Lab)
Fe- Mn powder 53.84 53.70 0.273 0.509
(Ita Lab)

All va lues in parenthesis are in jJg

* Average of fiv e determination s
# Masked with r
Therefore all the spectral measurements were carried determined by Job's continuous variation method and
out at this wavelength (Fig. 2) . mole ratio method and was furt her confirmed by
slope-ratio method, a plot of log D against log
Effect of equilibration period [PANH] at fixed pH (9 .0), where D is distribution
Th e colour development was instant, however ratio of manganese(II) between orga nic and aqueous
shaking time was varied from 5 to 120 s after reagent phase, and [PANH] is the concentration of reagent in
addition . The shaking time was fixed as 25 s for organic phase. A straight-line graph with a slope
extraction. There was no adverse effect on equal to 2, indicates I :2 (metal to ligand) complex
composition of complex or colour due to longer (Fig. 3)
equilibration time tried upto 120 s.
Effect of diverse ions
Extraction with various solvents Effects of various cations and anions on the
Manganese(II) was extracted with PANH in extractive separation of manganese(II) were studied
different solvents. The extraction was found to be and the tolerance limit was set as an amount required
quantitative with chloroform (99.63 %), while with to cause an error of ± 2 o/o in the manganese(li)
amy l acetate, ethyl acetate, n-butyl acetate, xylene, recovery. The tolerance limits for the diverse ions
toluene, benzene, carbon tetrachloride and isobutyl investigated are: F-, Cl-, Br-, I -, N0 3-, N02-. SO/-,
methyl ketone the extraction was found to be so/-, cio3-, Br03-, Io)-, co/ -, Hco)-, s2o/-.
incomplete (between 47.07-4.75 %). Therefore SCN- , acetate, citrate, tartrate, ox alate, urea (20 mg
chloroform was used as the solvent for further studies. each); S 20 52- (12 mg); S 20 82-, Li+, Na+, K+, Ca 2+,
Mg 2+, Ag+, Se4 +, Al 3+, Sb 3+, Bi+ (I 0 mg each); W 6+
Validity of Beer's law (7 .5 mg) ; S 20/- (6 mg); Mo 6+ (5 mg); Pt4+ (2 mg);
The present studies indicate that the system obeys Fe 3+, V 5+ (1 .5 mg each); Au 3+ (0.2 mg); Pd 2+ (0.15
Beer' s law in the concentration range 0.02-1.5 Jlg mg); Cr3+, CW (0.07 mg each); U6+ (0.025 mg) ;
mL- 1 of manganese(II). The molar absorptivity and EDTA (0.015 mg); Bi 3+ (0.005 mg) and interfering
Sandell's sensitivity of the system was found to be ions like Co2+, Ni 2+, Cu 2+, Zn 2+ are masked with CN-
4.606xl04 L mol- 1 cm- 1 and 1.19 ng cm-2 and Hg 2+ masked by I-.
respectively. The Ringbom's optimum working range
was 0.15-1.28Jlg mL- 1• References
I Deb K K & Mi shra R K, J Indian Chem Soc, 55 (3) (1 978)
Composition of the extracted species 289.
The composition of the extracted species was 2 Chikuma M, Nakaya Y, Yokoyama A, Maitani T & Tanaka
 PA WAR er al.: SPECTROPHOTOMETRIC DETERMINATION OF MANGANESE(II) BY PICOLINALDEHYDE 203

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