Association of Ions and Fractional Crystallization

A General Chemistry Experiment

Charles W. J. Scaifeand Richard L. Dubs
Union College, Schenectady, NY 12308

Several laboratory manuals describe experiments (1-4) Solubilities (Moles of Solute per 100 grams of Aqueous Solution)
utilizing a metathesis or double displacement reaction of two (8)
soluble salts to form two different soluble salts that can be
separated by fractional crystallization. In these experiments
solid sodium nitrate (NaN03) and potassium chloride (KC1)
are first dissolved in hot water. In principle, either of these
salts, along with potassium nitrate (KNOJ) and sodium
chloride (NaCI), can crvstallize from the resulting aqueous
+~~lutiun. 111 practice. changes otsduhiliry with ttniprrature
i a w r crvstnllizarim uf KNO whrn the aqueou~aulutiun ia
first cooled below room temperature and then crystallization
of NaCl if the volume is decreased by evaporation. Cooling and of authors (2,3) suggest rapid cooling' which makes it difficult
evaporation can be cycled several time; and either KN03 or to use shapes of crystals for identification.
NaCl can be crystallized a t each stage. This reaction is of . . of this uauer
The uurnose . . is to Present an exueriment that
practic;tl imp&nct. h:cause it p&allcla the induitrirll rimed previously hv u4ng culor a,
~.verconlist lie dillie~~lries
an additional charartt.ri,ti~ 11su,hi,,h <tt1dt111sw n t 1 l l 8 , w
prt.pttrittion uf K S O I I 1 frum ('llilr ralrpeter ! N a y 0 , I and
~ l r l l i \ V~vl\,ite
IKCIII. purification and identify cryst& of two soluble salts obtained
--.~~- ~~~, ~, thvever. student interr~rrtatim oiwhat
< -
from a metathesis reaction. A number of laboratory manuals
~ ~

takes place and understanding of the reasons for these oc-

currences are minimized because distinctive experimental
evidence for any of the salts is difficult to obtain. All four salts
are white solids and are not readily distinguishable in ap- degree of separation and the purity of crystals can be followed
easily hy ohst.rvin:: the appr:Ir,tIIw (gr disnpptaranct uf color.
pearance. Furthermore, all form colorless solutions so that
('dur i j 31s" a rhuri~(.tcriiticin nn exptrimcnt 171dw'ril,ing
there is no obvious visual means (except from disappearance
the growth of crystals. Ideas from these experiments stimu-
of solid) to determine when a sample is dissolved or how much
latcd us 11, find n metatheaisreactim in wh~chI W < , Cthr I I rw
of it is dissolved. luhr ialrr are n h r e d .prctl.ri~l~l\. :I ~lltfrret~t col<,r)and the
Several alternatives have been devised by previous authors other
- ~ - - t~w- ~ ~ a s l t s aI<SO
rr ~ I I I K('I
I~ nltieh inn he diatinruiahvd
to assist student interoretation and understanding, but each ~ ~ ~~~ ~ ~

easily by crystal shape. &ch a metathesis reaction tak& place

of them has a t least one disadvantage. Two sets of authors ( I ,
2) tell students which salt dominates each crop of crystals.
This leaves no uncertainty, but it eliminates the benefit of
students drawing their own conclusions. I t is more desirable
pedagogically fo; students to identify crystals from experi-
mental evidence, through considerable thought about solu-
bility graphs, or preferably both. A third set of authors (3) tells
students to identify each crop of crystals by means of quali-
tative analytical tests. The difficulty with this approach is that
students obtain more than trace positive tests for all four ions
in each crop unless several time-consuming purifications by
recrystallization are performed prior to the tests. The puri-
fications make the experiment unduly long and sidetrack
students from its primary thrust. A fourth set of authors (4)
tells students to identifv each crou of crvstals by means of
prrdictiona trum a iduhility gral~h.This is a nurthwhile ex-
rrcisr. but S I I I I I E I I I S ~ ~this level should proceed trmi cxwri-
ment t o theory rather than vice versa.- hey should be en-
couraged first to derive conclusions from experimental data
and then to try to understand their conclusions by comparison
with a solubility graph. In addition, while using a graphical
method for identification, many students fail to realize that
the concentrations of K+ and Nos- have been depleted by
crystallization of the previous crop unless they are prodded
to think about it by some experimental evidence. Finally, an
unpublished experiment (5) has students identify each crop
of crystals by comparing their shapes observed under a mag-
nifying glass with those of the four pure salts recrystallized
previously either by students or by the instructor. By this
method KN03 is identified easily by most students from the
needle-like crystals that are formed on slow cooling. Never-
when a 2 1 mole ratio of KC1 and hydrated nickel(I1) nitrate
[Ni(N03)26H20]is dissolved in aqueous solution.
The following experiment has been used in laboratories
both for nonscience majors and for inorganic chemistry stu-
dents in at least their third term. In both cases students attain
a good understanding of what is taking place, how the various
procedures affect actual concentrations of ions present, and
why particular salts crystallize under certain conditions
whereas others do not.
\Vithin thr enprrimenti, queatiama arc 3skt.d I U itimulate
audcnts 10 think mure ieriuuJy a h u t 11. Studr~ttsare ex-
pected tu r~mipletethe t i r ~ twu t s c r t ~ c m~ ' t l i ~xperimental
c
sevtiwi hefore c o m i n ~to thi, I ~ i h u r ~ ~ tTht. w v . h r ~ ~ utili~ed
un
is essentially that of ;eference (4).
Experimental Sectlon
Write two separate net ionic equations showing how Ni(N03)2and
KC1 dissociate into ions when dissolved in water. Write four separate
net ionic equations showing all possible ways in which these ions might
associate to form ionic compounds.
The solubilities at different temperatures for the four compounds
are given in Table 1. Plot the soluhility-temperaturedata for each
compound on the same graph. Which of the four compounds varies
most in solubility with an increase in temperature? Which varies
least? Which is the most soluble and which the least soluble at room
temperature? Which is the most soluble and which the least soluble
at 100°? At what temperature do KNOBand NiClz have the same
solubility? If equimolar amounts of the four ions are in solution and
' Presumably the purpose of rapid cooling is to prevent formation
of KC1 above 34' (where KC1 is less soluble than KNO,) that would
contaminate KNO- crvstals formed below 34' (where KNO" ~.is less ~ ~~~

theless, crystals of the other three salts cannot be differen- solub e lnan XCI) Tnis can also oe pre#enreo oy aissolwng mlially a
tiated by most students using this method. Moreover, two sets mass of XCl thal s oe ow ils soluoi ity I m I a1 34'.

418 Journal of Chemical Education

water is removed slowly a t 40". which compound do you expect to
crystallize first? Why?
T h e nickel salts are easily distinguished by color. Crystals of
Ni(NOs)2.6H20 are green; crystals of anhydrous NiC12, the dominant
form in this experiment, are yellow-brown; and crystals of hydrated
nickel(I1) chloride (NiC126HzO) are yellow-green. Although KNOJ
a n d KC1 cannot he distinguished by color since both are white, they
can be differentiated by the shapes of their crystals. Note carefully
t h e shapes of crystallized KNOs and KC1 provided by your in-
struet~r.~
\\'eigl~It!.:! f ur \ i SCJ ! .l,H.U and i.c; L .ji Kt'l t n r ., ~ ~ll!wrnl.
I,riArr..md . ~ d dI5 ntl. .tnnt(.r. iid*d ,111 a~ra~,lntl>.lit?gr:i),h, nhal
m l l ~ $ l r n l mlcml,rr.iturt mu-1 llc a , h $ t w d 1,. rli.+~.lvr. hllh u r n
pounds?
Warm the mixture with stirring until both solids are completely
dissolved. L e t the solution cool to room temperature, swirling it oe-
casionally. Observe and record physical characteristics of any crystals
that f o r m . V h e n cool the solution to near 0' bv olacine the beaker
in a n ice-water bath for 5 min to allow laree'&vstal>ruwth and
to wash the crystals.
Filter the cold solution rapidly using a Buchner funnel and suction.
With the aspirator off, add drapwise 4 mL of previously chilled wash
water so that all of the crvstals are moistened. Swirl the filter assembly
carefully to wash the cristals; then remove the water by suction. RL-
peat t h e washing using 3 mL of chilled water. Describe any changes
in physical characteristics of the crystals during w a ~ h i n gSave . ~ the
filtrate for a later step. Based on color and shape, which compound
crystallized? According to your solubility graph, which compound
crystallized? Why? Do your two conclusions agree? Why, or why
not?
If a solution containing Ki, Ni2+, NOs-, and C1- ions is evaporated
a t agiven temperature, and water is gradually driven off, thesolution
will eventuallv become saturated with r e s ~ e e to t one of the com-
1n ut.ds t l n ~ can l x i w n d I)! .( n . ~ ~ s < . r i ~ It iiw~ .m
qm. r . a l h ~i. coo-
I I ~ I dI , ~t h~ ~ t m ~ # ( u*dl n dc r y w I . k r m ~ ~ w n.n, gIU irtm
I. w l u ~ w n
'1 111 1 ~ 1 1 1 1 1i t m W I I I rrn..>iu III ~ d u t : mrind ulll invrc.lzc in ~tenccn-
tration as a result of the decrease of t h e volume of water.
Transfer the filtrate from the suction flask to a number 3 evapo-
If time and cost of chemicals permit, students can dissolve and
crystallize their own samples of KNO, and KCI.
Long needle-like crystals form on cooling to about 30'. Crystals
should be examined at this ooint because cwstals fwmed durino cwlina
in the ice-water bath are huch smaller duk to more -~ raoid fokation;
~-
~ ~ ~~ ~ ~~ ~~~~~~~~
~ 7 - -
%ltho,gn we do no1 normally req-ire sluaents lo dry and weign meir
crysta~lizeosamples. 7 0 " ~ol the poss ole KNO, (como neo firs1 an0
third crops) and 30% of the possible NiCI, (second crop) can be re-
covered.
Filtrate collects in the test tube rather than inthe suction flask from
which it must be transferred while hot to a s e m r a t e container.
How do you know?
Continue evaporating until a thin crust forms over the entire surface
of the solution. In the meantime, half fill a 500-mL suction flask with
warm water, and insert a 20 X 150 mm testtube into the flask followed
by a Biichner funneL5 Grasp t h e evaporating dish with a towel, and
suction filter the mixture rapidly while hot. Note the color of the
crystals on the filter and remaining in the evaporating dish.4 Based
on color, which compound crystallized? According t o your solubility
graph, which compound crystallized? Why? Do your two conclusions
aeree? Whv or whv not?
"..-"
that fnrm
.-.u..
Filter the cold solution rapidly using a Buchner funnel and suction.
Then wash the crystals with 2 mL of chilled water added dropwise.
Describe anv chanees in ohvsical characteristics of the crvstals.'How
do these crystals cnmpare with the first and second cropsof crystals?
Based on color and shape, which compound crystallized? According
to your solubility graph, which compound crystallized? Why? Do your
two conclusions agree? Why or why not?
Write a balanced molecular equation for the overall reaction you
have been able to carry out, starting with crystalline Ni(NO:Jz and
KCI. What two variables involving solubilities have you made use of
to force this reaction to the right?
Literature Cited
(1) Frmtx, Harper W., and Mdm, Lloyd E.. "The F~eemmLibrary of Laboratirryseparate
in Chemistry." W. H.Fieemanand Co.,San Francisco. 1970,"ol. I. 109S.
(2) Brescia, Frank, Arenb, John. Meidich. Herbert. Turk. Amos, and Weiner. Eugene,
'"Fundamentals of Chemistry: Laboratory Studios." 4th Ed., Academic Press. Ine..
New York, 19SO.p. 191.
(a) psge,,lnhnA , hi^^^^, ~ d A,, and
~ ~ ~ ~~M~~~E..
d ~*chemistry:
~ principles
~ t ~
and Experiments? Holt, Rinehart and Winston, b c . , New York. 1969, p. 44.
(41 Lauhenmyer,AW.,Scaife,C.W,J..andBeachley.Jr..O.T.."Exp~iimentsandProb-
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1972, p. 59.
151 Scaife. C. W. J., "Solubility and Ammiation of lone" in "Scientific Creativity: A
Chemistry Couae for Nonscience Majors that Is Entirely Lahuratory."Fourth Biennial
Conference on Chemied Education, Univ. of Wisconsin, Madison, 1976.99,
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Corporation, Lake Charles, LA, 1972. p. 19; Laubon~rye?,A. W., Scaife,C. W. J., and
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Hdt. Kinehartand Winston. he.. 1972.p. 23: Sienko. Michell J., and Plane, Robert
A . "Experiments1 Chemiatry,"4th Ed., McGraw~HillBook Co., Now York, 1972,p.
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General Chemistry."2nd Ed.. W. B. Saunders Co., Philadelphia, 1974, p. 147; slow^
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in Lhe Lsburatury,"3rd Ed., Saundera College Publishing, Philadelphia. L981, p. 9.
(71 D'Auria,JuhnM.,Gilchrist.Alan %and Johnstone. Joyce J.,"Chemi~tryand tho~n-
viionment: A Laboratory Experience." W. B. Saunders Cu., Philadelphia. 1973, p.
4...
2
( 8 ) Linke, William F., "Solubilities: lnorganie and Metal-Organic Compounds: 4th Ed.,
American Chemical Society, Washington, D.C., 1965, vol. 11, p. 114 (KCI), p. 250
(KNOs), p. 1208 [NilN03)21. p. 1216 (NiCI?).
Volume 60 Number 5 May 1983 419