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NEHOAANDUH REPOAT ARCCB.MN.gOO I O

DETERMINATION OF SOD'UM CYAN/,DE IN COPPER


AND CADMIUM CYANIDE PLATING SOLUTIOA'S

BY PRECIPITATION.FORMATION TITRATION

SAMUEL SOPOK

DTIC
,IARCH

'990

,ff0

TRilY ARIilIiIETT RESEARCII,


DETEIOPiIEIIT AIIII EII EI II EERI 1I C C EIITER
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I
I

OISCIAIMER

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docrrcnts.

of trade nanc(s) ard/or nnufacturcr(s)


an official indorsenent or approval
Tlrc usc

docs not conscitute

DESTRUCTIGi NOTIG

For classificd docuncnts, follow the procedues

Industrial sccurity Manual, section II-lg or

I}oD

in

DoD s2oo.22-t1,

s2oo.l-R, Info:ration

Security Progran Regulation, Chaptcr IX.

tnclassificd, linitcd docunents, destroy by ary nethod thst will


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stc

eponr oocutlENTATloN rlGE


ARCCB-a-900I0

;=;

REFoRT

PERloo covEto

a. flf LE (rd Sutlt')

TN COPPER
DETERMINAION OF SODIIJM CYA{IDE
BY
SOLUTIONS
PIATING
AND CADMIIJ}'! CYA}IDE
PRECIP ITATION-FORMATION TTTRATION

iEIxrttox

U.S.

ErG

A!,lCt,lS No. 6126. 23. 1BL0.OAP'


PRON No. I.O2ZRAENI'LSC

ArnY A3DEC

12. REPORf OATE

ffi^Ho^oonEss
Arff,Y

truraen

xaE

Benet laloratories, SMCAR-CCB-TL


wateti\rliet, NY 12189-405

U.S.

,ffi.nEPonr

March l99O

ARDEC

Close Conbat Armaments Center


UNCLA.SSIFIED

Approved

for public release' olst'ribution unltrriEed'


20' tl dttl'?at

@ocnGD")

Chenical AnalYsis

laa

Plating Solutions

Platinq Solutions
Titration
ion-Formation
PreciPitat

Cadnium CYanide

SodiLn CYanide

Copper Cyanide

ffirrtrDlocli'at

adequarelv
lacks an acceptable analvtical merhod ro
cadmirm-::::t:i*:tl:
d
detennine and monitor sodium cva'a-li coPper
::::ffiH i:"J:";;:i"n"ni""';;;:of this salt in these
*"it"ring-1"^:':il:':,T:'l:ui:
presented providing "."pi"r" .rr"ry=i" .r,a
cyanide are 58 g'l1
salun
plating nrocess.-.s.' *: ptin* o'.r"iir,i--t*g""-of
maxi.mum in copper .r.r,iu'n,;;i"; ="i:il;":I?1:-n1:-'.?:tTH
ranse of
in rhe :1"::T.,*
preclsiel:

.I;l:T.ff;

il"r..*"

ii'r'i",'"r:::

]}lH ;1.;::;':";il;:.'^il."l"lii.1ns

DO t

toL
,at rl

rm

or?o

o, t tloY

aS 13

o.lo|.Etc

. CONTID 1:"
ON RE:VERSE)

c?ror or'l'rat rlcgfD- D-.


ABSTIACT (COT.D)

'0.5 to 4.O g/L, prowiding adequate monitoring of these metal finishine


solutions sr4{pr:ted by six years of testing.

[,NCI.ASSIFIED
aCUtttV CLA3tFtCAftOX OF fXt3 ,AOClrr D... a..?.)

TAELE OF COIITEI{TS
Eese

ACKNOI{LEDGEMENTS

ITROOUCTION....

i
1

EXPERIHENTAL PROCEDURE

...

RESULTS ANO OISCUSSION

REF

EREI{cES

TABLES

:,

EXPERIHENTAL TITRATION CATA FOR THE SODIUM CYANIDE STANDARD


SOLUTION

:I.

IXPERII'IENTAL fITRATION OAA FOR SOOIUM CYANIDE


CYANIDE SAMPLE SOLUTIONS

IN

COPPER

III.

EXPERII,IENTAL fITRATION DATA FOR SO0IUtl CYANIDE


CYA}.IIDE SATPLE SOLUTIONS

IN

CAOMIUM

:V.

PRECISION

v.

PRECISION OF

5O-g/1 SOotUr{ CyANtO

VL

PRECISION OF

11-9/1 SILVER NITRATE TITRANT

VII.

PRECISION OF

A sO-m.I CLASS-A EURET

0F A 2-ml CLASS-A PIPET

STANOARO SOLUTION

SOLUTION

NTIS

GFA&I

u
n

DTI,C IB
Uannouced

i JusttflraLl
I

,-- frvalr ;Ed/oi


Dlst I Speotet

in,t I
idi-_t_
I

ACTilOXLEDGE!,IET{TS

Specia) thariks are given to E'l]en Fogarty and Rose Neifeld of Benet

;aboratories for their rssDective word processing and technical editing work on

th'is nanuscriot.

11

^l

IT{TROOUCTIOtr

Iiteratune Iacks an acceptab'le analytical

The chemical

method

to deternine

and monitor sodium cyanide in copper and cadmium cyan'ide plat'ing solutions in

the plating processes. Lack of optim'ization of these plating solutions

causes

serious problems for the me'ral finishing industry sueh as poor quality products
and wasted resources.

only

The

common

these solutions

chemica'l analysis method

is a co] or

to determine

test kit

comparison

cyanide in

sod'ium

such as the one Drovided by llerck

Corporation (ref 1), however, th'i s method provides poor precis.ions.

specific

The
and

mon'i

method described

in this report provides

acceptab'le analysis

toring of this salt in the meta.l f inish'i ng processes.

The method con-

sists or a precipitatioil-tormation ritration (refs 2,3). Re'lative precisions of


this method are in the raige of 2 to 3 peneent.
EXPERIIIEnIAL

PROCEOURE

Strict analytical chemistry


thls exoerimental

orocedure

rethods and orocedures


Two

sect.ion.

is by Fritz

An

are foi'lowed throughout

excellent source of reference for these

and Schenk

(ref 3).

analytical reagent grade standard solutions are required. The first

a 50 + 0.S-gt

tion),

methods and procedures

'1 sodium

and the second

cyanide solution

is a

1? 1

(l g/1

sodium hydroxide

0.1-gll si lver nitrate

t,i

trant

rs

for stabil iraso.l

ution.

These

:,{o solut'ions are prepared and standardized as described'in References 2 and 3.


Two

orher analytical reagents are required. The first is potassium iodide

indicator

powder and

The procedure

the second is concentrated

ammoni,m hydrox.ide

to prepare standard and sample solutions is the

solution.
same

for

the

solutions. This titration analysis requ.ires that


mi'l 'l i'l iters (ml ) of sanpie or standard solution i.s pipetted into a 400-mi
copper anc, cadmium cyanide

beaker.
and a

Then

the beaker is fil]ed to about the 100-ml mark with deionized v{ater

stirring bar is added. Also

iodtde'indicator
The

anc!

added

to this beaker is 0.1

gram

of

potassium

5 nl of concentrated ammoniun hydroxide solution.

solution is titrated using the si'lver nitrate titrant to a fa'int

turoid pernanent endpo'int, recording the

amount

ye11ow

of titrant dispensed in millili-

ters at the endgoint.

All standard

and samole solutions are analyzed

cyan'ide concentrations

in triplicate.

in the samo'les are calcul ated by normal

Sod'ium

chemical

stoiciliometry.
RESULTS ANO OISCUSSIOI{

Exoerimenta'l standard

solutions.

titration data are presented in Table I for

Experimenta'l sample

titration data are presented in Table II for

copper cyanide sample so] ut'i ons one and two and
sample

these

in Table III for

cadmium cyanide

solutions three and four. The titration can be summarized using the

fo!lowing equations. The f irst tvro involve the cyanide-si'l ver ion relationsh'io
ano the th'i

rd involves the iod'ioe-si lver ion endpoint indicator


Ag* * 2CN- <--> (Ag(CN)e)(Ag(CN)2)- + Ag+ <-->
Ag+

Sriver

cyan'icle

ammonium

ationship:
(1)
\)

2A9CN

(3)

AgI

vil'l not precipitate in these solutions due to the presence of

ions allowing on'ly the silver iodide to precipitate at the endpoint.

The calcu'lat'ion

original

* I- <-->

re'l

sample so'l

for determining the concentration of

sodium cyanide

in

the

utions is

g/'l

NaCN

= (50)(All(B)

()

where

A=n'l of titrant for


B

where
(

refs

the constant

Eq.

(4

standard

is the combined result of

many constants

2,3 ) .

Using Eq.
samo'le

ihe

va'l ue i n

titrant for

= m] of

samole

sodium cyan'ide values

for ccpper cyanide

solutions one and two in Table II are 35.1 and 49.9 g/1. Lirewise,

same

samo]e

(4), -he respective

rrsno

equation, the resoect'ive sodium cyanide vaiues for cadmium cyanidc

solutions three and foulin fable III are 84.9 and 140.1

gz1.

!t is useful to evaluate the variations in prec'ision for the materials and


rerhods ,lsed. Taoles IV through VII present the data for the 2-m'! c lass-A
oioets, 50-g; ! sod-um cyanide stanctard solution, 17-g/1 silver nitrate titrat
sojution, and the 50-ml class-A burets, respective'ly.
The data obtained

by this riethocl are sufficient to aclequately monitor the

sodiun cyanide'i n the meta'l finishing processes, thus prov'iding

efficient use of
resources. fhe opt'imum operating ranges of sodium cyan'ide are 58 q,l max:rnrm :n
the coooer cyanide platrng solrtions and 149 gr'1

maximum

in the caomium.:yan.:r)

oirting onl*.iions. he nesu'l t'ing precisions are in the range of 0.5 rc t.0 :.
orovioing adequate monitoring of these metal finishing solutions suoporteo bv
srx years of testing.

,a

REFEREIICES

t.

"EM Quant

Chlorine and Cyanide fests,"

Corooration, Cherry
2.

0. Peters, J.

H'i

Elt

Science Civision

of

Herck

l, NJ, 1980.

Hayes. and G. HieftJe, themiqal separatio-!_q_a!q.Measure-rnets:

Theorv and Prqglice

of Analytical

Chemistrv, W.

B.

Saunders

Company

ohl laclelphia, PA, |9?4.


3.

i. Fritz and G.
A1

Schenk,

q@cal

lyn and Bacon. Inc., Boston, l,tA,

Chen.istrv, Fif
198?

_^

th

Ectitron.

TAELE

Rep I

I.

EXPERI}TENTAL TITRATIOI DATA FOR THE


SOOIUI{ CYATIIOE STA}TOARO SOLUTIOil

Titrant

icates

Used (ml)

10. 2s

10. 20

10.20

((avgl

t0.22

r
_t

TABLE

II.

EXPERII{EilTAL TITRATIOII DATA FOR SOOIUil


CYAilIOE It{ COPPER CYA}IOE SAI'{PLE SOLUfIONS

i
Sample One
I - i '-nt Jsed
-----t---

Sample

(ml

Two

Iitrant Used (ml I

:<

10. 20

?. i5

10. 20

.20

10. 20

?.1?

10.20

TAELE

III.

EXPERII{ENTAL TITRATIOT{ DAA FOR SOOIU}I


CYAi|IDE Il CAOl,lIUl,l CYAiIIDE SAI'IPLE S0LUTIOI{S

----f
I

?eO; rCareS
I

Samg

le 'hree

--T-I

' _ :::_:':11.''''

Samole Forr

__L__""1: :'"0

i?.35

28. 60

1?.35

28,65

1?.35

28. 65

1?.35

28. 63

x(avg)

'*''

AELE

Rep l

IV.

PRECISIOT OF

A 2-MI CLASS.A

PIPET

2-ml Pipet
volume (ml)*

icate

2.01

i .99

.99

.99

.01

.00

x(avg)
Sn

.00

0.01

rvoiumes are ca lcu'! ated f rom the *eignt-vo.l ume


re,l ation_
shio -f a croetted deionlzed ater so'l ution corrected for
temoerature.
fAELE

V.

PRECISIO}I OF

A 5O.g/.I soolut

CYA}IIOE STAN0ARO soLUTIoI{


I

Reo l i

cate

Sodium Cyanide (OZt*

49. 9?

49. 99

9.99

50.01

50.00

50.02

X(avg)
Sn

*Sodi ur cyanide concentrat.ions

given in References 2 and 3.

50.00

a,o2

are :alculated.by

methods

TABLE

/I.

PRECISIOT{ C2

Repl

icate

A 77.9/ I SILVER I{ITRATE

Si'lver

TTRANT SOLUTIOT{

trat

N'i

1?.1

1?

t7 .2

16.8

16. 9

16.8

(avg)

17.0

.0

o.2

Sn

__J

*Srlver nrtrate concetrations are caculated by methods


Eiven in References 2 and 3.
TABLE

VII.

Rep I : cate

A sO.mI CLASS.A

24.9A

25.02

25.05

24.98

25. 05

Sn

BURET

Volume 11 *

'I

x(avg)

*Volumes are

PRECISION OF

.98

25.00
0.0

calculated from the Height-volume relationship of a contained deionized ,rater solution corrected
or temperature at a point one-half ful'l --25 rnt.

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