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An experimental investigation of the interchange of carbon monoxide and cyanide ion in zerovalent nickel compounds

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An experimental investigation of the interchange of carbon monoxide and cyanide ion in zerovalent nickel compounds

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Content AN EXPERIMENTAL INVESTIGATION OF THE INTERCHANGE OF
CARBON MONOXIDE AND CYANIDE ION IN
ZEROVALENT NICKEL COMPOUNDS
A Thesis
Presented to
the Faculty.of the Department of Chemistry
University of Southern California
In partial fulfillment
of the requirements for the Degree
Master of Science
by
June Chase Dayton
September 1947
UMI Number: EP41562
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This thesis, ‘written by
ffgasc Phase Day to n
under the guidance of hPM.... Faculty Committee,
and approved by a ll its members, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fulfill
ment of the requirements fo r the degree of
Master, of Science
H«WaPATMORE
Secretary
D ate January. 1948
Faculty Committee
Chairman
C O • \S-1£>
TABLE OF CONTENTS
CHAPTER PAGE
I. INTRODUCTION. TO THE PROBLEM .................. 1
II. ' HISTORICAL SURVEY ........... 3-.
III. PREPARATION AND PURIFICATION OF REAGENTS .... 6
IV. FORMATION AND ANALYSIS OF CARBONYL-CYANIDE
.COMPOUNDS OF ZEROVALENT NICKEL. .......... 10
V. EQUILIBRIUM STUDIES ON THE POTASSIUM CYANIDE-
NICKEL CARBONYL REACTION IN ACETONITRILE. .... 19
VI. PRELIMINARY STUDY OF THE CARBON MONOXIDE-
POTASSIUM TETRACYANONICKELATE (0) REACTION
IN ACETONITRILE................................. . 22
VII. DISCUSSION............... 23
Summary ..... .............. . . . . . . . . 2 6
BIBLIOGRAPHY................................................ 27
LIST OP PIGURES
PIC-URE
1. VAPOR TENSION OP NICKEL CARBONYL AS A FUNCTION
OP TEMPERATURE ...... ......................
2. MODIFIED APPARATUS USED FOR THE PREPARATION OF
' N
CARBONYL-CYANIDE COMPOUNDS....................
3. PINAL APPARATUS USED FOR THE PREPARATION OP
CARBONYL-CYANIDE COMPOUNDS ....................
PAGE
8
12
17
CHAPTER I
INTRODUCTION TO THE PROBLEM
Since the cyanide ion has an electronic structure
similar to that of carbon monoxide,
(:C:::N:)” :C:::0 :
it is often possible to form.compounds in which carbon mon
oxide has apparently been replaced by cyanide ion, as in
nickel carbonyl and potassium tetracyanonickelate (0):
Ni C C 0)4 K4Ni(CN)4
However, the zerovalent nickel cyanide compound is
much less stable in air and water than the carbonyl* K4Ni(CN)
decomposes Y/ater liberating hydrogen and forming potassium
cyanonickela.te (II), K^ITMCN)^; in air it oxidizes immediately
to black nickel oxide*1 On the other hand, nickel carbonyl
may be kept indefinitely under Y/ater protected from air.^ if
air is present slov/ oxidation to the carbonate and formate
occurs.^
The question arises as to the possibility of forming
intermediates between lii(C0)4 and K4Ni(CN)4 by the interchange
of carbon monoxide and cyanide ion. Such compounds might
1J. W. Eastes and W. M. Burgess, J. Am. Chem. Soc.,
64, 1189 (1942)
2M. Berthelot, Compt. rend. 112, 1344 (1891)
3A. A. Blanchard and W. L. Gilliland, J. Am. Chem.
Soc., 48, 874-8 (1926)
form upon the addition of potassium cyanide to nickel car
bonyl. A preliminary experiment indicated that a reaction of
some sort occurs. The nature of this research problem is to
investigate further the interchange of carbon monoxide and
cyanide as follows;
(1) By separating and analyzing the products formed
when nickel carbonyl reacts with potassium cyanide in some
suitable solvent.
(2) By determining whether an equilibrium situation
exists in the KCH-Ni(C0)4 reaction.
(3) By approaching the proposed equilibrium from the
reverse direction by adding CO to K4Ni(CN>4.
(4) By interpreting the results in relation to the
ability of CM” to replace CO in zerovalent nickel compounds.
CHAPTER II
HISTORICAL SURVEY
Manehot and Galibin reviewing certain nickel com
pounds note that with increase in valency of the central
atom, it Is easier to add cyanide ion and more difficult to
add carbon monoxide. This tendency can be illustrated with
the following series of compounds;
Hi11 Ni(CN)2 K2NI(CN)4
Ni1 NiCN NiCN(CO)x K2Hi(CN)3 KgNi(CK)3C0
Ni° Ni(C 0)4 K4Ni(CH)4
Divalent nickel forms the very stable cyanide, Hi(CH)g,
and the stable complex cyanide, KgNi(CN)4* Neither of these
compounds has been shown to add carbon monoxide or to ex
change, even partially, their cyanide for carbon monoxide.
Monovalent nickel, according to Manehot, picks up
carbon monoxide with more ease than does divalent nickel. He
believes that nickel (1) cyanide adds carbon monoxide to form
a compound of the formula, NiCN(GO)^. His conclusion is
based on a color change in a solution of "NiCH" when CO is
added with subsequent decomposition to Ni(C0)4 and Ni(CN)g.
He reports somewhat more detailed data on the addition com
pound of potassium cyanonickelite (I), KgNi(CN)3, and carbon
monoxide. When aqueous KgNi(CN)3 at -9°C is shaken with CO,
the volume of gas absorbed corresponds to a compound of the
Manehot and H. Gall, Ber., 59 (B), 1060-3 (1926)
formula,, KgHi(CN)3C0. However, this compound has not been
isolated.
Finely divided zerovalent metallic nickel readily
picks up pure carbon monoxide at room temperature and at
mospheric pressure.2 The direct addition of cyanide ion to
nickel, for instance nickel in the colloidal state, has not
as yet been tried although Ormont^ has suggested the idea.
The tetracyanide (0) compound is now made under more drastic
conditions— the addition of excess K to KgNi(CN)4 in liquid
ammonia solution.* The possibility of interchanging the
cyanide of K4Ni(CN}4 with carbon monoxide and the carbon
monoxide of nickel carbonyl with cyanide is under study in
the present investigation. The former interchange should
be easier than the latter if Manehot>s generalizations are
correct as to the greater ease of formation of zerovalent
nickel-carbonyl compounds over nickel-cyanide compounds.
The carbon monoxide in nickel carbonyl has already
been replaced by bases other than cyanide ion, notably pyri-
5
dine and o-phenanthroline. The replacement in the case of
pyridine is reversible. If carbon monoxide is removed as it
2L. Mond, C. Langer, and F. Quincke, J. Chem. Soc.,
57, 749 (1890)
3B. Ormont, Acta physicochim. U. R. S. S., 19,
571-5 (1944)
4J. W. Eastes and W. M. Burgess, Op. Cit. , p. 1188-9
5W. Hieber, F. Muhlbauer, E. A. Ehmann, Ber., 65 (B),
1098-1101 (1932)
5
forms, dark brown compounds crystallize out. These compounds,
which vary in composition with the temperature, the time of
4
reaction, and the method of drying have the formulas Hio(C0)^~
O
(C5H5N)2, Ni(C0)2(C5H5N), and Nl2 (C0)4(CgHgN)3* The reaction
of nickel carbonyl with o-phenanthroline proceeds more smooth
ly than with pyridine. If equimolar quantities of the two
reactants are combined in some suitable solvent, ruby red
crystals having the composition ITi(GO)g(C^gHgNg) come down.
As can be seen from the compounds discussed in this
chapter, nickel tends to co-ordinate four in monometallic
complex compounds. Even when the co-ordination number is
three, it increases to four if possible?
KgNi(CN)3 f GO — 4 KgNi(CN)3C0
K2H±(CN)3 + 110 —--» K2Ni(CN)3N06
Because of this tetra-coordination one would predict that if
cyanide-carbonyl compounds of zerovalent nickel form, they
would have one of the following formulas?
(Ni(C0}3CN)~ (Ni(CO)g(CN)g}“* * (Ni(CN) 3C0)“““
The formation of a complex ion of the formula, (Ni(C0)gCN)“,
would be unlikely in the presence of CO and CN~.
J. S. Anderson, Z.« anorg. allgem. Chem*, 229, 364
(1936)
CHAPTER III
PREPARATION AND PURIFICATION OF REAGENTS
All reagents used in the course of this investigation
were purified in the following manner;
potassium cyanide, potassium cyanide was obtained
in reagent grade and dried at 110°C to remove water.
Acetonitrile. Eastman Kodak acetonitrile, CH3CN, was
distilled from phosphorus pentoxide, P4O10. The fraction
boiling from 81.5 to 81.7°C was collected. Whenever the
acetonitrile was used in an experiment It was redistilled
from P4O1Q in a high vacuum apparatus. Its vapor tension at
25«0°C was 8.9 cm. which was identical with Heines value,^
Carbon monoxide. Carbon monoxide was made in the
high vacuum apparatus by adding boiled-out sulfuric acid to
air-free formic acid. The gas was passed through a ten-inch
tube of calcium chloride, ascarite, and P4O20 an(^ then through
a dry Ice trap. Since concentrated sulfuric acid when added
to concentrated formic acid forms only carbon monoxide, the
gas after drying was assumed pure.
Nickel carbonyl. Cylinder nickel carbonyl was ob
tained from the Mathieson Company. Three distillations from
\x. Heim, Bull. soc. chim. Belg. , 42, 467-82 (1933)
7
P4O10 ^he high vacuum apparatus at 0°C freed the carbonyl
from water and from iron carbonyls that may have formed in
the cylinder. To test the purity the vapor tension of nickel
carbonyl was measured as a function of temperature:
°A p in mm. 1/T log p-
288.0 259.7 3.47 x 10~3 2.414
287.2 250.0 3.48 2.398
286.1 240.9 3.50 2.382
284.1 217.1 3.52 2.337
278.8 173.2 3.58 2.239
273.0 134.0 3. 66 2.127
268.8 110.0 3.72 2.041
261.9 80.0 3.82 1.903
256.0 59.0 3.91 1.771
251.0 46.0 3.99 1.663
248.7 40.5 4.02 1.607
The plot of log p versus the reciprocal of the abso
lute temperature gives a straight line as shown in Figure 1.
The vapor tension equation calculated from the graph is:
log p ----» 7.53 - 1.47 x 103/T
It compares favorably with Anderson*s equation which covers
the range -35° to 45°G:^
log p ----* 7.690 - 1519/T
Both equations give the value 38.9 cm. for the vapor tension
of Hi(CO)4 at 25°C.
Potassium tetracyanonickelate (0). K4Ni(CH)4 was made
by the method of Eastes and Burgess3— metallic potassium was
added to a liquid ammonia solution of K2Hi(CH)4. Cylinder
2J. S. Anderson, J. Chem. Soc., 1656 (1930)
3J. W. Eastes and W..M. Burgess, Op. Cit. , p. 1188-9
~ yp utc
>P T
m
i?w40
9
ammonia was assumed to be dry and used directly.. The anhydrous
potassium cyanoniekelate (II) was prepared as recommended by
Pernelius.^ The lump potassium was a Baker and Adamson pro
duct.
In the presence of excess potassium as indicated by
a blue ammonia solution, a bulky precipitate of K^Ni(01^)4
forms. The precipitate that was obtained in this experiment
was copper colored when free of ammonia, black when exposed
to air. Eastes and Burgess report similar results. They
analyzed their compound with some diffictilty— not accounting
for as much as six per cent of the original sample weight in
some cases. There was a possibility that the compound might
not be completely free of K2Ni(CN)3 which could have formed
near the local excess of K2Hi(CN)4 when the lump of potassium
was first added despite vigorous magnetic stirring. This
objection could be overcome by pouring an ammonia solution of
K2Ni(CN)4 into a well stirred ammonia solution of potassium.
%. C. Fernelius, Ed., "Inorganic Synthesis", McGraw
Hill Book Company, Inc., Hew York 1946 Vol. II ed. 1.
p.227-8
CHAPTER IV
FORMATION AND ANALYSIS OF
CARBONYL-CYANIDE COMPOUNDS OF ZEROVALENT NICKEL
It was Pound that when nickel carbonyl was in contact
with potassium cyanide, a slow reaction took place. A gas
was given off and a yellow precipitate was mixed with the
solid potassium cyanide. The first problem was to find a
solvent that ?/ould dissolve both nickel carbonyl and potas
sium cyanide in order to speed up the reaction. To separate
the products from the potassium cyanide there must be a de
cided solubility differential in the solvent used.
It was difficult to find a solvent capable of dis
solving an inorganic compound, KCN, as well as a metallo-
organic compound, NI(C0)4# Methyl alcohol qualified in some
respects— it dissolved nickel carbonyl and dissolved 4.9 g.
KCN/lOO g. solvent at 19.5°C-1 - but there was always the pos
sibility that its active hydrogen might react with the pro
ducts. Acetonitrile proved more suitable. The solubility
of KCN in acetonitrile at 25°C, measured by evaporating the
solvent from a saturated solution, was 0.3 mg./g. CH^CN.
When acetonitrile was used as a reaction medium, the solution
turned yellow above the white crystals of potassium cyanide.
The second problem was to design an apparatus for
•*A« Seidell, "Solubilities of Inorganic and Metal
Organic Compotinds", Van Nostrand Company, Inc., New York
1940 Vol. I ed. 3. p. 718
11
the reaction. Since a gas is liberated a large volume would
\
be desirable# The first vessel was constructed out of a six
inch test tube surmounted by a sealed-on 500 cc, round bottoa
flask*
Potassium cyanide was put into the tube and the system
evacuated in a high vacuum apparatus* Acetonitrile and nickel
carbonyl were condensed at liquid nitrogen temperature upon
■the potassium cyanide and warmed to room temperature. Bub
bles formed and the solution turned yellow* After three days
the gas that would not condense in liquid nitrogen was evac
uated, The solution was decanted from the tube to the bulb*
With the tube in a horizontal position in the high vacuum ap
paratus the excess nickel carbonyl and solvent were distilled
off at room temperature. When almost dry the yellow residue
turned black. The next time when a lower distillation tem
perature (about -15°C) was used, a yellow and a yellow orange
product were left* Immediately on exposure to air the yellow
product turned black and the yellow orange product, which
was oapable of reducing bromine and silver nitrate, slowly
turned pale green*
Another experiment was performed using a similar but
slightly more complex apparatus, shown in Figure 2* Acetoni
trile (1*6570 g*) and nickel carbonyl (0*6081 g*) were con
densed upon potassium cyanide (0*1665 g*$* The unit was
sealed off at (A)* Several minutes after the solution warmed
up to room temperature bubbles of gas were observed. After
>= B
C.
FIGURE 2.
MODIFIED APPARATUS USED FOR THE PREPARATION OF
CARBONXL-CYANIDE COMPOUNDS
four days a small amount of white solid remained at the bot
tom of the yellow solution® The unit was put hack in the
2
high vacuum apparatus by using a tube opener on (B). The
amount of gas above the solution was assumed to be all the
gas that formed in the reaction.^ The volume of this gaseous
product that would not condense in liquid nitrogen was measured
in a Topler pump system. This volume, corresponding to 2.66 x
10“3 moles (assuming the ideal gas law holds), was passed
through two furnaces, a copper oxide furnace set at approxi
mately 615°C which oxidized hydrogen to water and carbon to
carbon dioxide and a copper furnace set at 220°C which picked
up oxygen. The issuing gases were passed through a liquid
nitrogen trap and the uncondensed portion recirculated until
a constant amount of uncondensable gas, 0.03 x 10“ ^ moles, was
left. After the liquid nitrogen bath was replaced by a dry .
ice-ether bath, the volume of gas was remeasured. There was
now 2.73 x 10* ”' 5 moles of gas present (evidently carbon di
oxide). No drops of water were visible in the trap after the
dry ice bath was removed. These results indicate that essen
tially all of the original gas was carbon monoxide.
The original unit was sealed off under vacuum at (C)
and the solution decanted from the tube to the bulb. After
2Stock, A.j "Hydrides of Boron and Silicon", Cornell
University Press, Ithaca, New York. 1933 p. 180
rz
^The solubility of carbon monoxide in methyl alcohol,
the solvent most like acetonitrile on which measurements have
been made, would be negligible at the pressures involved as
shown by G-. Just, Z. physik. Chem., 37, 361 (1901)
14
standing at room temperature for several days, the bulb was
inserted horizontally into the high vacuum apparatus by using
a tube opener on (D). A small amount of gas had formed dur
ing this period. With the bulb in an ice-salt bath at -15°C,
the excess solvent and carbonyl -were distilled off and weighed.
Of the 1.8071 g. of material recovered, 0.1501 g. would be
nickel carbonyl if a complete recovery of the acetonitrile
were assumed.
The unit was sealed off at (E) and transferred to a
dry-box through which nitrogen was passing. The bulb was
broken and several 4 mm. sample tubes were immediately filled
with the solid product and sealed. A carbon-hydrogen analysis
on this yellow solid gave 18.6 per cent carbon (which usually
runs low when the carbon is present as carbon monoxide) and
0.446 per cent hydrogen (which usually runs high). This small
percentage of hydrogen indicated that acetonitrile neither
took part in the reaction nor appreciably solvated the pro
ducts. The other samples were used to determine cyanide,
nickel, and potassium.
The method of analysis for cyanide was tried success
fully on pure KgNi. ( 01^)4, a material thought to be as close in
composition to the product as could be obtained. Excess 0.1 N
silver nitrate-was added to 0.1 g. sample of K2Ni (CN^.HgO
in a 100 ml. volumetric flask. The flask was, diluted to the
mark with 0.1 N nitric acid. After the silver nitrate had
settled, ten ml. of the supernatant liquid was titrated with
15
0.1 N potassium thiocyanate using two ml. of a saturated solu
tion of ferric ammonium sulfate as indicator. When the method
was applied to the unknown, the silver nitrate was reduced and
the sample weights available were too small to give accurate
results. The first difficulty could be overcome by dissolving
the unknown in acid and then adding the. silver nitrate. The
samples which weighed from 10 to 20 mg. gave percentages of
cyanide ranging from 8 to 17. Later, analyses made on 40 and
90 mg. samples both gave 12.2 per cent cyanide.
Potassium and nickel were determined gravimetrically.
Potassium was determined by the sodium cobaltinitrite method.4
The results ranged from 18 to 28 per cent potassium on 25 mg.
samples. Nickel, determined as nickel dimethylglyoxime,
ranged from 20 to 22 per cent on 20 mg. samples.
When the above analyses for cyanide, potassium, and
nickel \*/ere carried out, the odor of nickel carbonyl could
be detected after opening the sample tube. This loss of
nickel made it imperative to find a method of analysis that
would give consistent and accurate results for nickel, potas
sium and also carbon monoxide. The percentage of cyanide
could be deduced from the percentage of potassium since moles
of cyanide must be equal to moles of-potassium— there are no
other possibilities for positive and negative ions as long
as the valence of nickel remains zero. To solve these ana
lytical problems the apparatus was redesigned as shown in
4L. V. Wilcox, Ind. Eng. Chem. Anal. Ed. 9_, 137 (1937)
U niversity of Southern C alifornia U lw rw
Pi glare 3.
After several grams of KCN had been placed in the
tube at (A) (see Figure 3), part (1) was sealed to part (2).
The unit was joined to the high vacuum apparatus at (B).
Acetonitrile (5.058 g.) and nickel carbonyl (1.4078';g.) were
condensed upon the potassium cyanide at liquid nitrogen tem
perature. The stopcock at (C) was closed and the unit left at
25°C for three days. After the gas that would not condense
at liquid nitrogen temperatures v/as evacuated,.the tube was
sealed off at (D). The solution was carefully decanted into
the three small bulbs (3), (4), and (5). The weight of each
bulb to the ground glass joint was known and the volume cal
ibrated to (E). The tube was reinserted into the vacuum ap
paratus by using a tube opener on (P). The small bulbs were
kept in an ice-salt bath while excess carbonyl and solvent
were removed. When no more solvent could be removed, the
bulb' (3) containing a yellow product was sealed off at (E).
After half hour periods the other two bulbs, (4) and then
(5), were sealed off. To determine the weight of product
the bulb and the remaining part up to the ground glass joint
were weighed. The samples weighed from three to five tenths
of a gram. The sample, bulbs were inserted into the high
vacuum apparatus by means of a tube opener. A furnace at
200°C was placed around the bulb and the volume of evolved
carbon monoxide measured in a Topler pump system. Apparently
nickel carbonyl was given off when the compound decomposed
3.
FIGURE 3.
FINAL APPARATUS USED FOR TEE PREPARATION OF
CARBONTL-CfANIDE COMPOUNDS
thermally because the carbonyl collected in a trap placed
between the sample and the pump. The carbonyl was decomposed
by means of a gas flame. The residual nickel in the trap was
combined with the black residue in the sample tube, dissolved
in concentrated hydrochloric acid and transferred to a 100 ml,
volumetric flask. Ten ml, aliquot portions were evaporated
to dryness and then analyzed for potassium and nickel.
The following percentages ?/ere obtained on analyzing
the three sample tubes (cyanide was calculated from potassium)
(3) (4) (5) ave,
foCir 13,5 17.3 17,1 15.9
foK 19.9 26.1 25,7 23.9
f o i l1 27.4 25.9 25.7 26.7
%C0 34.2 31.3 41.2 35.6
3T73 lUtJTS 10977 10271
The percentages indicate a composition represented empiri
cally as K5Ni4 (GN)5 (CO) Undoubtedly, other experiments
would indicate the formation of mixtures of slightly dif
ferent composition.
CHAPTER ¥
EQUILIBRIUM STUDIES ON THE POTASSIUM CYANIDE-
NICKEL CARBONYL REACTION IN ACETONITRILE
In order to clarify further the NI(C0)4-KCN reaction
equilibrium studies were undertaken. It was necessary to
establish the presence of an equilibrium between the gaseous
product, CO, and the reactants. The apparatus consisted of
a 50 ml. round bottom flask equipped with a magnetic stirrer
and attached to the high vacuum apparatus as well as to a
mercury manometer which could be used with the comparison
arm either in vacuum or at atmospheric pressure* Several
grams of KCN were placed in the bulb,and the reaction vessel
immediately sealed in place. Acetonitrile (2.8235 g.) and
nickel carbonyl (0.5000 g.) were condensed upon the potassium
cyanide. Shortly after the bulb had been immersed in a 25.0
■ f 0.5°C bath, bubbles were observed to form as the solution
turned yellow. The following day, approximately ten hours
later, the solution was very pale yellow and a yellow pre
cipitate was present. Periodic readings of the pressure in
crease were taken until the total pressure exceeded the
capacity of the absolute manometer. At this time (38 Hours
after the reaction had started) the compaidson arm was opened
to the atmosphere. The pressure read 107.1 cm. in a volume
of 100 cc. The pressure differential then dropped until no
further readings could be taken without the entrance of
20
mercury into the sample tube# The pressure (18 hours after
the manometer had been opened to the atmosphere) was 88 cm.
in a volume of 87 cc. This reversal in CO pressure strongly
indicates an equilibrium.
Since the system appeared to reach an equilibrium,
a study was made of pressures developed by varying concen
trations of nickel carbonyl in acetonitrile always in the
presence of a large amount of solid potassium cyanide. The
following data give the weights of nickel carbonyl and
acetonitrile used, the equilibrium pressures developed, and
the volume of the system at equilibrium:
g. CHgCN g. Ni(CO)4 p in cm. vol. in cc
2.4989 0.5155 121.5 106
2.3474 0.3533 84.4 115
2.3386 0.2289 61.5 109
2.3381 0.1433 44.4 87
2.5131 0.1124 36.7 98
2.7971 0.0507 22.'2 91
4.0667 0.0181 13.5 75
Nickel carbonyl was still present at the end of the experi-
rnent and this observation meant that the gas at equilibrium
probably contained acetonitrile , carbon monoxide and nickel
carbonyl. In an attempt to determine what fraction of the
pressure was CO the vapor tensions of nickel carbonyl-aceto-
nitrile mixtures were measured as follows:
g. CHgCN g. Ni(C0)4 , p in cm. vol. in cc,
2.6627 0.0000 8.9 91.0
0.0190 10.0 91.4
0.1080 13.4 92.9
0.2309 17.4 94.5
0.3525 22.1 96.3
0.5283 26.3 97.9
0.6645 29.7 99.3
21
Prom the data at hand the definite CO pressures are
not kno\, m but their range can be calculated. For instance,
a solution of nickel carbonyl (0.516 g.) in acetonitrile
(2.500 g.) has a vapor tension of about 27 cm. When such a
solution reacts with potassium cyanide the pressure developed
at equilibrium is 121 cm. The minimum CO pressure would be
27 cm. less than the observed value of 121 cm., or 94 cm.
Actually, the CO pressure is higher because as some of the
nickel carbonyl reacts its partial pressure over the solu-
tion decreases. The maximum pressure which would develop
if 8.11 the nickel carbonyl reacted would be 121 cm, minus
the 9 cm. pressure of acetonitrile, or 112 cm. There would
be 5.4 x 10”3 moles of CO at 94 cm. and 6.4 x 10“' - ’ moles
at 112 cm. Since 3.0 x 10“3 moles of nickel carbonyl were -
added, from one to two carbon monoxide molecules were re
placed per nickel atom.
CHAPTER VI
PRELIMINARY STUDY OP THE CARBON MONOXIDE-
POTASSIUM TETRACYANONICKELATE (0) REACTION IN ACETONITRILE
A preliminary experiment was made to determine whether
an equilibrium was established on the addition of carbon mon
oxide to potassium tetracyanonickelate (0) in acetonitrile.
About four cc. of CH^CN were condensed upon K^_Ni(CN)^ which
was in a tube attached to a manometer in the high vacuum
apparatus. A small amount of gas was evolved and the solu
tion turned pale yellow, but no change in the appearance of
the excess solid K^Ni(CN)^ was noticeable. After once evac
uating the gas, no more formed. About an atmosphere of car
bon monoxide, 72.6 cm., was admitted above the solution
which was held at a constant temperature by a thermostat at
25.0 + 0.5°C. The pressure decreased slowly for several days
until it reached 65.4 cm. During this period a white residue
deposited out of solution on the sides of the reaction tube.
Solid copper colored tetracyanonickelate (0) plus a yellow
precipitate were left on the bottom of the tube.
To determine whether the system was in equilibrium
the pressure was increased to 67.2 cm. After several days
the pressure remained constant at 65.6 cm., or approximately
the same pressure as was first developed.
No attempt v/as made to separate the products.
CHAPTER VII
DISCUSSION
The extent of the Interchange of the carbon monoxide
in nickel carbonyl with cyanide was not conclusively deter
mined. However, carbon monoxide definitely is replaced.
When the KCN-Ni(C0)4 reaction was carried out in a large vol
ume apparatus, with a large excess of nickel carbonyl, and the
solid residue was obtained by vacuum distillation of excess
solvent and carbonyl at -15°C, the product contained from two
to three carbon monoxide molecules per nickel atom. This
means that the mole ratio of replaced carbon monoxide to
nickel carbonyl destroyed was between one and two. The ana
lysis indicated that one of the empirical formulas was
IGjNi^CNjg(CO)n. Logical guesses can be put forth as to
the identity of the constituents. There must be nickel in
the compound present in some form other than nickel carbonyl
since carbon monoxide is given off and metallic nickel is not
present; this nickel must be zerovalent since there is no way
for it to be oxidized. These facts, along with the solubility
of the products in acetonitrile, the decomposition of the pro
ducts in vacuo at room temperature, and the bringing into
solution of so much potassium and cyanide (considering the
meagre solubility of potassium cyanide in acetonitrile) can
be explained best by assuming the formation of monometallic
nickel complex compounds with co-ordination of four. The
24
mixture might then consist of KNiCN(C0)3 and KgNi(CN)g(CO)g.
Such compounds would have large anions of small charge den
sity— a circumstance which would contribute to their solu
bility in acetonitrile, an organic solvent with a dielectric
constant of 39. Other types.of compounds might be suggested
such as dimetallic nickel complex compounds or carbon monoxide-
bridged nickel carbonyls; however, they could not account for
the presence of so much potassium and cyanide in solution.
Before the identity of the compounds is certain, they
should be isolated. During the course of this investigation
there was not time enough to undertake this separation. In
any case, it is difficult to suggest a solvent that would
dissolve KNiCN(CO)g and not KgNi(CN)g(CO)g| consequently, it
might be necessary to separate them by fractional crystalli
zation from acetonitrile— a task that would not be easy to
perform in the absence of air and at sufficiently low tem
peratures. The study of the absorption spectra might aid in
the identification of the products, provided these compounds
are different enough to permit interpretation of the results.
An insoluble product seems to form when the volume
of the reaction tube is small and the amount of solid potas- • .
sium cyanide is large.^Although a yellow precipitate comes
down, the amount of gas present at equilibrium still indicates
between one and two carbon monoxide molecules are being re
placed per nickel carbonyl molecule. The equilibrium results
show that the carbon monoxide pressure increases with increas
25
ing nickel carbonyl concentration in acetonitrile, always in
the presence of a large excess of potassium cyanide*
Further study is necessary before the.exact relation
ship between the concentration of nickel carbonyl and the
pressure of carbon monoxide at equilibrium .can be calculated*
An analysis of the gas at equilibrium should be* made; a separ
ation and analysis of the yellow solid should be carried out;
i
the solubilities of the products in acetonitrile should be
measured. With the resulting data it might be possible to
calculate an equilibrium constant for the reaction.
The reversibility of the Hi(C0)4-KCN-CH3CN equi
librium was indicated by the absorption of CO by K4Ni(CH)4
in CI-IgCH. However, if KgNi (CN) 3 were present as an impurity
in KgNi(CU)3, it might pick up CO at 25^C. Before the true
significance of this experiment can be determined, the follow
ing investigations should be made;
(1) The CO and K4Ni(CH)4 should be analyzed.
(2) The residual gas should be analyzed to ascer
tain if it is still pure CO or if it is mixed with hydrogen.
(3) The apparatus should be equipped with a stirrer
capable of thoroughly mixing the gas and the solution.
(4) The'solubility of CO and K4Hi(CH)4 in CH3CN
should be determined. If K4Ni(CN)4 is not very soluble and
the products are more so, it should be possible to decant the
solution and subsequently separate the products by evaporation
of the solvent.
26
(5) An analysis of the products should be made to
see if this equilibrium is identical with the KCN-Ni(CO)^ one.
(6). The equilibrium should be studied by setting up
a series of reactions with varying initial CO pressures and
noting the change in pressxire.
SUMMARY
Nickel carbonyl reacts with potassium cyanide in
acetonitrile to form carbon monoxide and zerovalent nickel
compounds that were not individually isolated. A typical
mixed product gave an analysis corresponding to an empirical
composition of K^Ni^ (CN) 5(00) material has reducing'
properties, is soluble in acetonitrile, and decomposes in
vacuo at room temperature.
The reaction comes to equilibrium after several days.
In successive experiments -with increasing Ni(CO)A concentra
tion there was a marked increase in CO pressure.
Prom the analyses and the equilibrium studies it
appears that from one to two molecules of carbon monoxide per
molecule of nickel carbonyl are replaced with cyanide.
The reversibility of this reaction is suggested by the
absorption of carbon monoxide by K^Ni(CN)^ in acetonitrile,
BIBLIOGRAPHY
BIBLIOGRAPHY
A. BOOKS
Fernelius, W. C., "Inorganic'Synthesis", McGraw Hill Book
Company, Inc., New York. 1946 Vol. II ed.'p. 227-8
Seidell, A., "Solubilities of Inorganic and Metal Organic ■ .
Compounds", Van Nostrand Company, Inc., New York. 1940
Vol. I ed. 3 p. 718
Stock, A., "Hydrides of Boron and Silicon",'Cornell Univer
sity Press, Ithaca, New York* 1933 p. 180
B. PERIODICALS
Anderson, J. S., "Die Einwirkung des Stickoxyds auf Nickel-
carbonyl", 3. anorg. allgem. Chem., 229, 357-68 (1936)
Anderson, J. S., "The Vapor pressure of Nickel Carbonyl",
J. Chem. Soc., 1653-6 (1930)
Berthelot, M., "Sur une combinaison volatile de fer et dtoxyde
de carbone, le fer-carbonyle, et sur le nickel-carbonyl",
Compt. rend. 112, 1343-9 (1891)
Blanchard, A. A. and W. L. Gilliland, "The Constitution of
Nickel Carbonyl and the Nature of Secondary Valence",
J. Am. Chem. Soc., 48, 872-82 (1926)
Eastes, J. W. and W. M. Burgess, "A study of the Products
Obtained by the Reducing Action of Metals upon Salts
in Liquid Ammonia Solutions. VII The Reduction of
Complex Nickel Cyanides; Mono-valent Nickel", J. Am.
Chem. Soc., 64, 1187-9 (1942)
Heim, G., "Vapor tensions and latent heat of vaporization of
some normal nitriles", Bull. soc. chim. Belg., 42, 467-82
(1933)
Hieber, W., F. ffiuhlbauer, and E. A. Ehmann,. "Derivate des
Kobalt-und Nickelcarbonyls", Ber., 65, (B), 1090-1101
(1932)
29
Just, G., uLoslichkeit von Gasen in organischen Losungsmitteln",
Z. physik. Chem., 37, 361 (1901)
Manchot, W. and H. Gall, "Zur Charakterisierung der Metall-
carbonyle: Tiber eine Carbonyl-Yerbindung des ein-
wertigen Nickels", Ber., 59 (B), 1060-3 (1926)
Mond, L*, C. Langer, and'F. Quincke, "Action of Carbon Mon
oxide on Nickel", J* Chem. Soc. 57, 749-53 (1890)
Ormont, B., "Existence of a New Type of Chemical Compounds'—
the Cyanyls", Acta physicochim. U. R. S. S., 19, 571-5
(1944)
Wilcox, L. V*, "Determination of potassium", Ind. Eng, Chem.
Anal. Ed., 9, 136-8 (1937)
U n iv e rs ity of Southern California Library

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Asset Metadata

Creator Dayton, June C (author)

Core Title An experimental investigation of the interchange of carbon monoxide and cyanide ion in zerovalent nickel compounds

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, inorganic,OAI-PMH Harvest

Language English

Contributor Digitized by ProQuest (provenance)

Advisor Burg, Anton B. (committee chair), Copeland, C.S. (committee member), Wilmarth, W.K. (committee member)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-790776

Unique identifier UC11348099

Identifier EP41562.pdf (filename),usctheses-c17-790776 (legacy record id)

Legacy Identifier EP41562.pdf

Dmrecord 790776

Document Type Thesis

Rights Dayton, June C.

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA