Sds 23r
Sds 23r
SD0100019
UNIVERSITY OF KHARTOUM
FACULTY OF EDUCATION
DEPARTMENT OF CHEMISTRY
JUNE 2000
Content:
Section One
Historical
Chapter One
Some Aspects of Tin Chemistry
Introduction :
(1-1) Elemental Tin.
(1-2)Bonds Forming.
(1-3) The Nature of (Sn-O)Bond .
(1-4) Synthesis of Tin Alkoxides.
(l-4-l)The Direct Route.
(l-4-2)The Reaction between Tetrachlorosilane and Alcohol.
(l-4-3)The Reaction between Tintetrachloide and Sodium
Ethoxide.
(l-4-4)Other Methods.
(1-5) Double Alkoxides of Tin.
(1-6) Uses of Metal Alkoxides .
Chapter Two
Section Two
Experimental
Chapter Three
Experimental
(3) Experimental.
(3-1) General Techniques & Procedures .
(3-1-1) Infra-Red Spectrum.
(3-l-2)Gas-Liquid Chromatography.
(3-2) Starting Materials.
(3-2-l)Ethanol.
(3-2-2)Tin Foil.
(3-2-3)Tin Tetra Chloride.
(3-2-4)Sodium Metal.
(3-2-5)Mercury(I) Chloride.
(3-3)Reaction Procedure & Apparatus .
(3-3-1 )The Reaction between Tin Foil & Dry Ethanol Using
Mercury(I) Chloride Catalyst.
(3-3-2)The Reaction between Anhydrous Stannic Chloride with
Dry Ethanol.
Section Three
Discussion
Chapter Five
Discussion
(5) Discussion.
(5-1) The Reaction between Tin Foil & Dry Ethanol Using
Mercury© Chloride Catalyst.
(5-2)The Reaction between Anhydrous Stannic Chloride with
Dry Ethanol.
(5-3)The Reaction between Sodium Ethoxide and Stannic
Chloride in presence of Ethanol.
(5-4)Comparison between Tin Ethoxides Produced by the Three
Different Methods.
Conclusion.
References.
Abstract
HISTORICAL
CHAPTER ONE
Sn + 2HC1 • SnCl2 + H2 t
i .
Tin is slowly attacked by cold sulphuric acid, but the hot
concentrated acid attacks the metal forming stannic sulfate and
sulphur dioxide(39). ;
No. of Isotopes 10 5
Cubic Tetragonal
Me Me
Me Me
The vacant 5d-orbital, gives tin the ability to form the partial
Tc-bond with groups that have extra pairs of electrons unshared in
a-bonding. The monomeric nature of silicon and germanium
alkoxides in contrast to analogous tin derivatives may be ascribed
to stronger P n - dn bonding in the former whibh diminishes in
germanium and appear to be insignificant in case of tin
alkoxides(7)
Tin can form bridged structures, involving five coordinate of
many compounds (R3SnX)(11).
Where : R = alkyl group X = halide.
Some tin alkoxides are polymeric with bridged alkoxy
groups(4), when tin bears more electronegative substituents, its
Lewis acidity increasing and coordination with d-electron rich
sites lead to sp3d or sp2d2 hybridization(9). There exist compounds
in which more than nine tin atoms may be linked together in the
form of branches or rings(11).
R Cl Cl !~H ~~CPt Cl
/ \ \ \ /
-> Si (-HC1) O—» Si
/ \ * / / \
IH Cli Cl R RO Cl
RO Cl RO Q
(-HCD Si and so on . Si
y x
/ \
RO Cl RO OR
Or . . « .
3NaSn2(OC2H5)9 + SnCl3(OC2H5).C2H5OH
10
from the small amount of sodium chloride contaminated with it.
Davies reported(7) his unsuccessful attempts to synthesize butyl tin
tri-alkoxides by the reactions of butyl tin trichloride with sodium
alkoxides. He observed only partial replacement of chlorine in
butyl tin chloride with sodium methoxide which finally yield
dichloride mono-methoxide.
11
The dialkyl distannoxane on being heated in vaccuo yielded
the volatile diakyl tin dialkoxide and a residue of diakyl tin oxide.
C2H5O OC2H5
V 7
Sn
12
Alkyl tin trialkoxides have been more recently synthesized again
by the reaction of alkyl tin trisdiethyl amide with alcohols.
Thomas(7) utilized this method for preparation of Sn(OPri)4. Pi^OH
from Sn(NMe2V The alcohol and the dialkyl amine formed in the
reaction mixture was fractionated out with a hydrocarbon solvent
or with alcohol itself.
Loberth and Kula(7) carried out the alcoholysis reactions of
alkyl tin tris (diakyl amide) for the preparation of number of alkyl
tin trialkoxides.
Gaur(7) prepared mono-alkyl tin chloride alkoxides by the
reaction of alkyl tin chloride with the corresponding alkyl tin tri-
isopropoxide in different stoichmetric ratios :
2RSnCl3 +
RSnCl3 + 2RSn(OPri)3
Dialkyl tin monochloride monomethoxide have also been
prepared by the reaction of dialkyl tin dichloride and the
corresponding dialkyl tin dimethoxide(7):
R2SnCl2 + R2Sn(OMe)2 • 2R2Sn(OMe)Cl
Alkyl tin alkoxides are prepared from the corresponding
alkyl tin hydride and alcohol in the presence of zinc chloride
catalyst.
13
1.5. Double Alkoxides of Tin :
Double metal alkoxides are believed to be prepared by the
following(7) :-
(1) Reaction of alkali alkoxides with another metal alkoxides:
U(OEt)5 + NaOEt ^NaU(OEt)6
(2) Reaction of metal halides with potassium, sodium or aluminum
wo-propoxides:
2SnCl4 + 9Na(OPri) • NaSn2(OPri)9 +8NaCl
(3) alcoholysis reactions :
M(OR)n +R3"SiOH ^==±M(OSiR 3 ") n . x (OR) n +xROH
The double alkoxides of alkali metal and tin MSn(OPr1)9
(M =Li, Na) are non volatile and appear to disproportionate in the
following manner on being heated under reduced pressure(7).
heat SnCOPA + MOPr1
MS^OPr1) heat fc 2Sn(OPri)4 + MOPr1
However, these derivatives have been purified by
crystallization from fro-propanol.
Table 1.5. Physical Properties of Some Ethoxides and
Double Ethoxide of Tin, Sodium(32)
Alkoxide Colour, form m.p, °C b.p. °C Solubility
14
1.6. Uses of Metal Alkoxides:
Metal alkoxides have advantages because of their catalytic
properties, ease of hydrolysis, solubility in organic solvents and
distillability.
They are mainly used as catalysts (in ziegler polymerization,
trans esterification and condensations) with partial or complete
hydrolysis, alcoholysis or trans-esterification in coating for plastic,
textile, glass and metals, and in additives for adhensives and paints
and for the cross-linking or hardening of natural and synthetic
materials(32).
Alkoxides are valuable precursors to metal oxides through
hydrolysis, pyrolysis or combustion. High purity of metal
alkoxides offer advantage, as starting materials for the preparation
of high purity oxides with high surface areas with the volatile
alcohol and the absence of ionic impurities(7). The hydrolysis was
very effective for depositing oxide films on graphite and in
producing powders and fibers of ultra-high purity ceramic
materials. High purity specialized glass films(32).
Tin alkoxides act as a source of nucleophiles, compounds
containing (Sn-O-C) bond were usedfortrimerisationofphenyl
wocyanate phNCO and ethyl /socyanate EtNCO(2). Tin alkoxides
,/also used in manufacture of some insecticides.
15
CHAPTER TWO
16
2.1. Physical Properties of Tin Alkoxides:
Tin alkoxides of primary alcohols are non volatile and
presemably polymeric with bridging alkoxy groups but the tertiary
alkoxides are monomeric and distilled easily at reduced
pressure(4).Tin alkoxides appear to be thermally less stable than the
corresponding silicon and germanium, all normal alkoxides of tin
undergo decomposition on being heated under reduced pressure(7).
Boiling 166°C/760 ~ 32
Pt(°C/mm)
17
2.2. Infra-red Spectrum of Tin Alkoxides :
The IR region of the electromagnetic spectrum extends from
0.8um (800nm) to 1000um(lnm)and subdivided into near IR
(0.8-2um), middle m (2-15um) and far IR (15-1000 urn). The
fundamental regionjpetween (2 and 15 um).IR spectroscopy can
be used for both qualitative and quantitative analysis, metal
alkoxides can identify by qualitative analysis only. Metal
alkoxides M(0R) (R : alkyl) exhibit v(CO) at Ca. 1000 cm"1 and
v(M0) at 600 - 300 cm"1(37). v(CO) for alkoxides, is in the region
1200 - 950cm"1 for (CH3)2 Sn(OCH3)2(27).
Four sets of bands in the region 700 - 500 cm"1 due to
various v(Sn-C) and v(Sn-O) stretching vibrations was observed(7).
The bands observed at about 700 and 670 cm"1 have been assigned
to (Sn-CH2) rocking vibrations arising due to gauche and trans
conformations respectively. The other bands observed at about
500 and 600cm"1 have been assigned to Vs and Vas (Sn-C)
stretching vibrations respectively. The band observed at 500 cm-1
was assumed to be associated with (Sn-O) stretching mode also
but there is no clear distinction between v(Sn-C) and v(Sn-O)
stretching vibrations due to their coupling(7).
Gaur studied(7). alkyl tin trialkoxides supported the above
view and also assigned the strong bands due to v(C-O)Sn in the
range 1030-1070cm"1 in primary alkoxides which shift to (940 -
980cm"1) in isopropoxide.
18
Table 2.2.1. Vibrational Spectrum of Alcohol
19
2.3. Gas-Liquid Chromatosraphv ofAlkoxides:
Gas liquid chromatography is used for volatile mixture requires
separation of the components, it shows the number of components
and the relative quantities of each. Although it is limited to
volatile materials, GLC working at temperatures up to 450°C and
this give the possibility of converting many materials into a
volatile derivative extend the applicability of separation.
GLC is the most powerful technique for the rapid and
convenient analysis of the composition of mixture of organic
compounds. It is based on the partition of components between a
mobile gas phase and stationary liquid phase retained as a surface
layer on a suitable solid supporting medium. There are many
columns thatoreused for separation of alkoxides the important one
is OV17 which is 1.5 long, fitted at 140°C. Another one is (OV-
101) on chromsorb W, 2 meter column(38) FID the flame
ionization detector the most used for organo-metal £ompounds(23)
The retention times for the separated peaks can be calculated
by measuring the distance between the starting point and the
middle of each peak. The area under each peak is relative with the
concentration of the component, it can be calculated by
determining the height of the peak in cm and the base of the peak
in cm and applied base data in the relation(39)
20
2.4. Some Selected Chemical Properties of Tin Alkoxides:
1. Hydrolysis Reactions(7):
The hydrolysis of metal alkoxides readily leads to the formation
of the hydroxides or hydrated oxides. When restricted amounts
of water are added, these metal alkoxides undergo partial
hydrolysis reactions yielding in same cases products of definite
composition as oxide alkoxides MOn(OR)x.
The hydrolysis of tin ethoxide was carried put in acidic,
basic and acid-base medium. A white gel was formed
and varied in time according to the type of the medium.
In acidic medium the formation of the gel was observed
first then in acid-base medium and thirdly in basic
medium. The mechanism of the hydrolysis as follow :
(1) In presence of hydrochloric acid (H+)
21
(2)In presence of base such as sodium hydroxide :
v
(EtO)n— Sn— OH + EtO ()
(ii)EtO w + H 2 O — • EtOH + OH ()
n = integer from 1-5 .
22
diacetate was finally obtained .The reaction appeared to proceed in
two stages as is illustrated by the following equation:
Sn(OBul)4 + 4CH3COC1 ^ SnCl4 + 4CH3COOBut
SnCl4 + 2CH3COOBul • SnCl2(OCOCH3)2 + 2Bu< Cl
23
The alkoxides of silicon are materials which cover a wide
range in applications. The alkoxides of it are well known of their
availability. The early studies discovered that the alkoxides of
other elements of group(iv) have similar importance as that of
silicon. They can be used instead of silicon alkoxides because
they have similar properties and even better than silicon itself.
Tin alkoxides have been widely used in industry as a
suitable precursor for synthesis. They are used for producing
building materials similar to natural stone from sintered glass or
sintered glass ceramic. They are also used in the formation of an
electrically conductive transparent coating or transparent
dielectric materials. They polymerize to form tin-oxygen bonds.
The co-polymer of them like indium-tin oxide is used in
preparing a layer uses as coatings, inks, a substrate e.g. glass,
ceramic, plastics. The introduction of sucrose residues into
organo-tin pesticides substantially increased the biological
activity per unit weight of tin, in addition the compound are very
c
effective against fungi.
Tin alkoxides are important materials in industrial
societies. Every year there are tenths researchers come out with
new utilities of tin alkoxides. The current work is concern of
preparing tin ethoxide by different methods. The study takes tin
alkoxides as independent unit without comparing it with silicon
alkoxides except in few cases. Some characteristic and physical
24
properties are taken on consideration. Therefore, the objectives
of the present work are as follows :
1-To investigate some routes of preparing tin ethoxides and
follow up- the growth of the products.
2-To study the effect of some variables parameters on the
growth of the products.
25
SECTION TWO
EXPERIMENTAL
CHAPTER THREE
EXPERIMENTAL
26
Guard tube (containing CaCL)
Condenser
Dropping funnel
Thermometer
Round-bottomed flask
Parameter Description
Column OV101 ,
Program 150°-280°C
Injected Volume 2M
Attenuation 128X1O3X1
28
3.2. Starting Materials:
The following chemicalsjjised as theyjpackaged.
3.2.1. Ethanol (Ethyl alcohol):
99.5% v/v dry ethanol had been used
Molecular weight 46 molarity 17.117.
m.p. -115°C density (at 20) 0.787.
b.p. 78.3°C
3.2.2. Tin Foil:
The percentage of its compound(4).
Sn% Cu% Pb% Sb%
88 3 8 1
29
3.2.4. Sodium Metal:
Bright silvery metal, very reactive metal, float on water, kept
in paraffin oil, m.p 97.81, b.p. 882.90., atomic weight 2, valency 1
3.2.5. Mercury (l) Chloride :
A white powder, supplied by BDH chemicals
molecular weight 472.,09 density 7.15
m.p. 400 i
insoluble in alcohol, ether, toxic & it was used as received .
3.3. Reaction Procedure and Apparatus:
The starting materials were put in a cleaned 3-necked round
bottom flask. A reflux condenser was vertically connected from
one side to central neck of the round bottom flask and the other
side was connected to a guard tube containing CaCl2 and glass
wool to avoid atmospheric moisture. One side neck of the round
bottom flask was fitted with a thermometer, the other side neck
was fitted with stopper and was used for adding the starting
materials by using dropping funnel. The system was refluxed at
certain temperature and degree of stir for specific time using hot
plate magnetic stirrer. (Fig.3.3 ) .
3.3.1 The Reaction between Tin Foil and Anhydrous Ethanol
using Mercury m Chloride as Catalyst:
A. The surface of tin was activated by scratching the above
layer of tin with sand paper. (2.9927g) of tin was cut into small
pieces and placed into 3-necked round bottom flask. Absolute
ethanol (150cm3, 2.5676M) was added one portion .Mercury(i)
chloride (0.057lg) was added to the content of the round
bottom flask . The system was refluxed at 80°C and 100 rpm
stir. ;
t
30
reaction mixture was filtered to separate the unreacted tuCThe
remainder solution was distilled at atmospheric pressure to
separate the ethanol at temperature range 78° - 80°. The residue
was small white precipitate. The distilled ethanol and the
precipitate which dissolved in absolute ethanoj were analyzed
by IR spectrum and shown by (Fig. 4.1.1 &Table 4.1.1. ) and
(Fig 4.1.2 & Table 4.1.2.) .The solubility and melting point for
the solid product were tested(See 4.4.1 & 4.5).
C. The same reaction was repeated again using (2.9953g) of tin,
ethyl alcohol (100 cm3,1.7117M) and tinny amount of Hg2Cl2
at 100°C and 300 rpm stir. The hot plate magnetic stirrer was
stopped at the first night, then it was continued work during the
later nights. Samples of solution (0.2 cm3) were taken
periodically with a pipette during the j"eac;tipj.. The final
reaction mixture was filtered and the remained ethanol was
separated. The residue was small tiny white precipitate. The
samples and products were analyzed by IR spectrum. (Fig.
4.1.3.1. and Fig. 4.1.3.2) . And also analyzed by GLC spectrum
(Fig. 4.1.4 to Fig. 4.1.8 ; Table 4.1.4.) .The solubility of the
solid product was tested in ethanol and the test of melting point
was done (See 4.4.1 and 4.5).
31
3.3.2 Reaction between Anhydrous Stannic Chloride with
Absolute Ethanol:
A. Absolute ethyl alcohol (100 cm3, 1.7117M) was placed into
3-neck round bottom flask (Fig. 3.3.). Anhydrous stannic
chloride (SnCl4) (25 cm3,0.2125M) was added to ethyl alcohol
using dropping runnel. The addition wasdropwise from one
side neck for an hour. White fumes were observed inside the
round bottom flask during the addition of SriCU. This white
fumes tested with litmus and it was changed into red. After that
the reaction mixture was refluxed at 80°C and 100 rpm stir for
six hours. The colour of the solution was pale yellow at the end
of the reaction.
The reaction mixture was distilled at atmospheric pressure into :
l)The first portion was collected at the range 78 - 80°C.
2)The second portion was collected at the range 90 - 120°C.
3)The third portion was dark yellow, cooled under room
temperature turn into dark yellow solid. The solid was
dried and turn into white solid. The product fractions
were analyzed by IR spectrum.
Fraction (i) (Fig. 4.2.1. and Table 4.2.1.).
Fraction (n) (Fig 4.2.2., Table 4.2.2.).
k
Fraction (in) (Fig. 4.2.3. Table 4.2.3).
The solubility and melting point were tested for solid
fraction (See 4.4.2. & 4.5.).
B. The reaction was.repeated using the same amount of starting
materials. The stannic chloride was added one portion. The system
was refluxed at 100°C and 300 rpm stir for 12 hours. Samples of
the reaction mixture were taken periodically.
32
The reaction mixture was distilled at atmospheric pressure into
two portions.
(1) The first portion was collected at the range 78 - 80°C.
(2) No portion was collected until 130°C, the remainder WPS
dark yellow solution which turn into white solid, samples and
products were analyzed by IR spectrum.(Fig. 4.2.4.1. and I'ig.
4.2.4.2.). And also GLC spectrum was used for analysis (See
33
3.3.3 The Reaction between Sodium Ethoxide and
Stannic Chloride in presence of Ethanol
This experiment contain two parts :
1. Formation of sodium ethoxide by the direct reaction
between sodium metal and absolute ethanol.
2. Exchange metal reaction between the prepared sodium
ethoxide from the above reaction and stannic chloride in
the presence of ethanol.
3.3.3.1.The Reaction between Sodium Metal and Absolute Ethanol
A. Absolute ethanol (100 cm3,1.7117M) was placed in round
bottom flask (Fig. 3.3.) . Sodium metal (1.0048 g) was cut into
small pieces, dried with fine paper and added to ethanol piece by
piece until all pieces were added. The reaction mixture was
refluxed at 80°C and 100 rpm stir for VA hour. Samples (0.2 cm3)
were taken periodically for analysis. After stopping the system, the
unreacted ethanol was distilled at the range 78-80°C. The
remainder was yellow solution dissolved in small amount of
ethanol. The system was kept closed for the sebond part of the
reaction. The samples were analyzed by IR and <3LC techniques
(Fig. 4.3.1. & table 4.3.1& Fig 4.3.3.1) and (Fig.4.3.4 & Table
4.3.5.).
3.3.3.2. The Reaction between Sodium Ethoxide and
Stannic Chloride in the Presence of Ethanol
The product of experiment (Fig. 3.3.3.1) was used for this
reaction in the same closed system. Using the dropping funnel
from one side neck of the round bottom flask, (5 cm3,0.0425M) of
dried stannic chloride was added. A vigorous reaction was
occurred. An immediate white fumes and white precipitate were
appeared . The reaction mixture was refluxed at 80°C and 100 rpm
stir to expel the gas for one hour. Samples (0.2cm3) were taken
periodically.
34
The final reaction mixture was filtered to separate ethanol at
temperature range 78 - 80°C. All the solution was distilled, IR
spectrum and GLC technique were used to analysis the samples
and products (Fig.4.3.2. & Table 4.3.2 & Fig.4.3.3.2 ) and (Fig
4.3.5.to Fig.4.3.6.& Table 4.3.2). The white precipitate was dried
and weighed. The solubility and melting point were tested.(See
4.4.3 & 4.5.)
B. The above experiment was repeated^in the first part (3.3.3.1).
The absolute ethanol was dried using calcium oxide before using
it, 100 cm3 was taken, sodium metal (1.95235g) was cut into
small pieces and cleaned in petroleum spirit then add to the
ethanol piece by piece. The reaction mixture was refluxed for an
hour. The mixture was distilled at the range 78 - 80°C. The
remainder was pale yellow solution.
The second part the addition of dried stannic chloride
occurred in steps first (3cm3) then (7 cm3). White1 precipitate was
formed immediately. The solubility and melting point were tested.
(See 4.4.3 & 4.5.)
35
The following relations were used in the
calculations :
36
CHAPTER FOUR
37
Fig. (4.1.1.)
Infra-red Specfrum of Distilled Ethanol Collected at range78~80°C
of the Reaction (B) between Ethanol and Tin Metal
00
if)
I
Table 4.1.1. (Fig. 4.1.1) Infra-Red Spectrum of Distilled
Ethanol Collected at Range 78-80°C
Of Reaction (B) between Ethanol &
Tin Metal.
s : strong
b : broad
w : weak
* : hydrogen bonding caused shift in the frequency.
39
fig. (4.1.2.)
Tnfra-red Spectrum of Product Dissolved in Ethanol
of the Reaction (3) betvteen Ethanol an«l Tin Metel
4000 3000 2000 v/AVENUHBEfc (err 1 ) woo 9oo Soo 709
f t * r > • > • 1. • 111, •. 1 1 . /1 / 1 1 1 * 1 1 . • 1 1 1 1 1 » 1 1 1 'i 1
2
Table 4.1.2. (Fig. 4.1.2) Infra-Red Spectrum of Product
Dissolved in Ethanol of Reaction (B)
between Ethanol and Tin Metal.
s : strong >
b : broad
w : weak
* : hydrogen bonding caused shift in the frequency.
41
Variations of Sn—p bond measured by I.R. spectroscopy, in the
reaction between tin foil and absolute etlutnol in the presence of
mercurous cliloridc as a catalyst at 100°C and 300° stir, with time.
The peaks were taken at the range 845 - 1250 cm"1.
4-3
44
No. Time (hour) I.K. Spectrum
Fig. 9 After Nine
Fig. 10
stopping the
reaction for
fifteen
Fig.13 Thirty
hours After
Restarting
Fig.16 Ninety
hours After
Restarting
Fig.17 Hundred
and Ten
hours. After
Restarting
• - v • ' ' • • ' • • • ' • • ' • • ' • .
'No*- Time (hour) I.R Spectrum
Fig.18 ^Product
Distillation
(dissolved •
in absolute
ethanol)
r
• . . • '.•- , f • . : ' : . • •'•,• • • " \ • : ? '
Fig.19 -Distiiiated
.'•<ne?Ranges|;?
i
The analysis of the products of the reaction between tin foil and
absolute ethanol in presence of mercurous chloride at 100°C and
300° stir by I.R. spectroscopy. The peaks were taken at the range
(845 -1250 cm1).
No. Sample
Fig. 1 Product
Dissolved in
Ethanol
Fig. 2 Distillated
Ethanol
Fig. 3 Absolute
Ethanol
Fig. (44.40
GLC Chroma tograrn of sample (A) of ike
between Tin Melal and absolute Ef$jan<sl
18
CLC C h r o m a t o g r a m of sample (B) o f the Reaction
Tin Metal and ah«;nfute ^ t h l
61
Fig. )
GLC Chromatogra/n ofsample ( Q of IKeHeadion
befiVeen Tin Metal rt»^ absolute Ethanol
Pig.
GLC Chroma togram of sample (D) of the Reaction
between Tin Metal and absolute Eihanol
S3
Fig. (4.1.8.)
GLC CJircmatogratfl of sample (E) of the Re
between Tin Metal and absolute Cthano
54-
Table 4.1.4. Results of GLC of Samples of the Reaction
between Tin Metal and Absolute Ethanol
in presence of Hg2Cl2 as Catalyst
55
Table 4.2.1. (Fig. 4.2.1.) Infra-Red Spectrum for Distilled
Ethanol at Range 78 - 80°C for
Reaction (A) between Stannic
Chloride and Ethanol.
vs very strong
s strong
w weak
m : moderate
* hydrogen bonding caused shift in the frequency.
57
Fig. (4.2.1.)
Infra-red Spedrum of Stannic Chloride Collected at range 90- 120°C
of the Reaction (A) between Stannfc Chloride and EthanoL
Table 4.2.2. (Fig. 4.2.2.) Infra-Red Spectrum for Fraction
Collected at 90-120°C for
Reaction (A) between Stannic
Chloride & Ethanol.
b : broad
w : weak
s : strong
* : hydrogen bonding caused shift in the frequency.
59
Infira-red Spectrum of Product Dissolved In Ethanoi
of the Reaction (A) between Stannic Chloride and FthanoL
(or1) 'too
l f l i l } l * t t t t |
too
I I I I I >V » »
700
I I . I I
f f •>•! ' I t I < I > I I
II
1 able 4.2.3. (Fig. 4.2.3.) Infra-Red Spectrum for Product
Dissolved in Ethanol of Reaction (A)
between Stannic Chloride and
Ethanol.
vs very strong
s strong
w weak
m moderate
b : broad
• hydrogen bonding caused shift in the frequency.
61
"3 (4-2-4--IJ
£2,
No. Time (hour) , LR. Spectrum
Fig. 3 After Three !
(A-
Tlie analysis of the products of the reaction behveen anhydrous
stannic chloride and absolute cthanol at 100°(! and 300° stir by I.R.
spectroseopy. The peaks were taken at the range S45 - 125(1 cnfJ.
Fig. 2 Product
Dissolved in
Ethanol
Fig. 3 Distillated
Ethanol
Fig. 4 Absolute
Ethanol
Fig.
GLC Chromatogram ofsampteCF) of the. Reaction
between Stamaic CKloride and absolute EtKanot
10 V
Fig. (4.2,6.)
GLC Chroma togra m of sample C<3)of the Reactfoh
between Stannic Chloride and absolute Ethanol I
Fig. C4.17J
CLC Chroma togrann of sample (H) of the Reaction
bh S f c Chloride and «aL^ula Ei>iai»ol
Fig. &2.S.)
GLC Chromatograna of sample (I) ofihe. Reaction
l E l
Fig. (4.2,9.)
GLC Chromatogram of sample (J) of the Reaciion
between Siannic Chloride and absolute Ethanol
Table 4.2.5. Results of GLC of Samples of the Reaction
between Stannic Chloride and Ethanol.
s : strong
vs : very strong
b : broad
* : hydrogen bonding caused shift in the frequency.
32)
Infra-red Spectrum of Product Dissolv ed in Ethanol of the
Reaction (AJ between Stannicckloridei iw the Presence qf EthanaL
900 %QO
±L-J i u, _: ) • I i i i i i—._ L_i i I I I i • ' ' • • ' • ' • * i i. I i i_
- > /
Table 4.3.2. (Fig. 4.3.2.) Infra-Red Spectrum of the Product
Dissolved in Ethanol of Reaction (A)
between Sodium Ethoxide and Stannic
Chloride in the Presence Ethanol
s strong
vs •very strong
b : broad
w weak
* : hydrogen bonding caused shift in the frequency.
- (4-3.3-1)
Variations of Na—O bond measured by I.R. spectroscope in the
reaction between sodium metal and absolute cfh;rnol a t 10fl°C and
100. stir, with time. The peaks were taken at the range
845-1250 cm-4.
Fig.2 After
Thirty
Alter Forty
•ive
No. Time (niin) I.R, Spedrurvi
Fig. 4 After Sixtv
Fig. 5 After
Seventy
Five
Fig. 6 After
Ninety
Fig. 7 Product in
Absolute
Ethanol
Variations of S n - O bond measured by I.R. spectroscopy, in the
reaction between anhydrous stannic cliloride and sodium et}ioxide
at 100°C and 100 stir, with time. The peaks were taken at the range
845-1250 cm 1 .
Fig. 1 After
Fifteen
Fig. 2 After
Thirty
\ 1 ^
Fig. 3 After Forty
• F i v e : "•••
~No7 Tiine (min) I.R. Spectrum
Fig. 4 After Sixty
Fia.5 Alter
Seventy
Five
Fig. 6 After
Ninety
-:? Q
/ (•••
Kg. (43.4,)
, GLC Chromalogra/h of sample CK) of the Reactuon
between Sodium Metal amJ absolute Ethanol
Fig. 04.3.5.)
QLC diromatogrann of sample (/V) of the Reaction
between Sodium trhoxide ancl Stannic Chloride
in the preSeTTce of Eihano
Fig. (4.3.6.)
GhC Chromatogram of sample (|v[) of the Reaction
Solvent Solubility
Ethanol Readily soluble
Distilled water Soluble and white
ppt. was formed
Time (Hours) 50
Temperature (°C) 80
Stir (rpm) 100
Solid reactant weight /g Ethanol volume /cm3
After reaction 3.3500 110
Before reaction 3.0498 150
The difference 0.3002 40
Reactant Product
Tin Ethanol
Weig No. of No. of Volu No. of Weight
htin moles moles me moles in
gram Cm3 grams
s
Theoretical 2.992 0.0252 0.1008 5.8889 0.0252 7.527
ly 7
Practically 0.178 0.0015 0.006 0.3505 0.0.015 0.448
Percentage 5.95%
Table 4.7.3. Summary and Results of Reaction (B) between
Tin metal and Absolute Ethanol Catalysed by
Mercury (I) Chloride.
Parameter Condition
Time (hours) 45
Temperature °C go
Stir (rpm) 100
Solid reactant Ethanol Solid product
weight /g volume /cm3 weight/g
Before reaction 1.0075 100 0.0
After reaction - 60 0.0421
Reactant Product
Tin Ethanol
No. of No. of No. of Volume No. of Weight/g
grams moles moles cm3 moles
.Theoretically 1.0075 0.0085 0.0340 1.9836 0.0085 2.5390
Practically 0.0119 0.0001 0.0006 0.0329 0.0001 0.0421
Percentage 1.658%
Table 4.7.5.Summary and Results of Reaction (C)
between Tin Metal and Absolute Ethanol
Catalysed by Mercury(I) Chloride
Parameter Condition
Time (hours) 117
Temperature °C 100
Stir (rpm) 300
Solid reactant Ethanol volume Solid product
weight /g cm3 weight/g
Before reaction 2.9927 100 0.0
After reaction - 50 0.5382
Reactant Product
Tin Ethanol
No. of No. of No. of Volume No. of Weight/g
grams moles moles Cm3 moles
Theoretically 2.9927 0.0252 0.1008 5.8889 0.0252 7.527
Practically 0.2136 0.0018 0.0072 0.4206 0.0018 0.5382
Percentage 7.15%
Table 4.8.1. Summary and Results of Reaction (A)
between Tin Tetrachloride and Absolute Ethanol
Parameter Condition
Time (hours) 6
Temperature °C 80
Stir (rpm) 100
Reactant Product weight/g
stannic chloride Ethanol
3
volume cm volume cm3
Before reaction 25 100 0.0
After reaction - 60 23.829
Reactant Product
Tin Ethanol
No. of No. of No. of Volume No. of Weight/g
grams moles moles Cm3 moles
Theoretically 25 0.2125 49.658 0.85 0.2125 63.474
Practically 9.388 0.0798 18.64 0.319 0.0798 23.829
Percentage 37.54%
Table 4.8.3. Summary and Results of Reaction (B)
between Tin Tetrachloride and Absolute Ethanol
Parameter Condition
Time (hours) 12
Temperature °C WO
Stir (rpm) 300
Reactant Solid product
Stannic volume Ethanol volume weight/g
3
cm cm3
Before reaction 25 100 00
After reaction - 60 26.0431
Reactant Product
Tin Ethanol
No. of No. of No. of Volume No. of Weight/g
grams moles moles Cm 3 moles
Theoretically 2.9927 0.0252 0.1008 5.8889 0.0252 7.527
Practically 0.2136 0.0018 0.0072 0.4206 0.0018 0.5382
Percentage 7.15%
90
Table 4.9.1. Summary and Results of Reaction 3.3.3.(B)
Parameter Condition
Time (hours) 1
Temperature °C 100
Stir (rpm) 300
Reactant Product weight/g
Na/g Ethanol SnC14 --
3
cm cm3
Before I 1.9523 100
After I - 62
II 10 6.0788
Reactant Product
Sodium Stannic chloride Complex NaCl
ethoxide
No. of No. Weight
moles of No.of Volume No.of (g) No.of Weight
moles. moles (g)
moles Cm3 moles
Theo 0.0849 0.0849 0.0189 2.2196 0.0094 6.255 0.0754 4.411
ritica
lly
tact- — — 0.0106 1.2471 0.0053 3.498 0.042 2.467
ically
Perce- 55.92
ntage
91
Table 4.9.3.: Summary and Results of reaction 3.3.3. (A)
H
Parameter Condition Parameter Condition
Time in hours l>5 Time in hours 1.5
(
Temperature °C • SO Temperature °C SO
Stir 100 Stir 100
Na Ethanol Weight of Volume of
weight volume product SnCl cm3
(g) cm3 A
Before 1.0048 100 -- 5
reaction
After 60 3.0502 am
reaction
Reactant
Product
Na Metal Ethanol
No.of No.of No.of Volume No.of
grams moles moles Cm3 moles
Reactant Product
Sodium Stannic Complex Sodium
Ethoxide Chloride Chloride
No. of No. of Volume No. of Weight No. of Weight
moles Moles CnP moles (g) moles (g)
Theoretically 0.0437 0.0097 1.1425 0.0086 3.234 0.0319
2.28
Practically 0.0239 0.0053 0.624 0.624 0.0027 1.775
0.022
Percentage 54.89
SECTION THREE
DISCUSSION
CHAPTER FIVE
Discussion
94
S.Discussion:
95
Mercury(i) chloride was suitable catalyst to accelerate the
rate of the reaction . The ion exist* as a dimer Hg + _Hg + ,
and does not dissolve in ethanol , therefore , it was
believed that it attacked by the upper oxide layer of tin to
give the i
Sn(OEt )2
Tin(n) Ethoxide
Or
Sn (OC2H5)2 + 4 C2H5OH
[ (OC2H5)3-Sn-O-Sn (OC2H5) 3]
Table 5.1.2. The Percent Area under the Peaks of Samples of the
Reaction between Tin Metal and Ethanol using
Mercury (I) Chloride as Catalyst.
98
5.2. The Reaction between Stannic Chloride and Absolute
Ethanol
Stannic chloride was added to absolute ethanol, a white
fumes was appeared which was assumed to be hydrogen
chloride gas. Stannic chloride firstly dissolved in ethanol. The
system was refluxed for six hours, then the reaction mixture was
distilled into three fractions, (i), (ii), (in) . Fraction (in) was
white solid which believed to be the product. The three fractions
were analyzed using IR spectrum. Fraction (i) , which was
collected at the range 78-80°C was suggested to be ethanol.
Fraction(ii) ,which was collected at the range 90-120°C was un-
reacted stannic chloride, while fraction (111) which was
dissolved in absolute ethanol for analysis showed the existence
of (Sn-O) bond at wave numbers 1031 ,1000,990 cm-1 this
emphasis the formation of tin ethoxide [See Fig. 4.2.1 & Table
4.2.1] , [See Fig 4.2.2 & Table 4.2.2 ] and [See Fig 4.2.3 &
Table 4.2.3 ]. Thus stannic chloride could react with absolute
ethanol according to the following equation :
99
followed with time by taking a sample periodically for analysis
by IR spectrum. The IR spectrum was taken at the range 845-
1250 cm-i [Fig.4.2.4.2 ] showed that the solid tin ethoxide had
more than fourteen small peaks. That small peaks were
interfered with (C-O) and (C-C) stretching peaks when the solid
dissolved in ethanol. The growth of the peaks was followed up
with time in the range 845-1250 cnr1. The number of the peaks
started growing on increasing the time . Thus, the formation of
tin ethoxide was directly proportional with time through this
method of reaction. The mechanism of the reaction was
suggested to be as that proposed for the reaction of silicon
chloride and ethanol as follows :
C1
Et Cl Cl ,_H _?ii
^O > Sn (-HC1) O > Sn
/ \
fH Cf\ Cl Et EtO Cl
100
The samples and product were analyzed using GLC [Fig.
4.2.5 to 4.2.9] .Peaks we/* appeared 5the retention time(RT)
were determined and areas under the peaks were calculated for
each samples, [Table 4.2.5]. Peak No. 1 was suggested for
ethanol according to the reference [Fig.4.3.7 ]. Peak No. 2 and
peak No.3 were suggested for tin ethoxide . All samples and
product chromatograms had the same peaks with approximately
similar retention times [Table 5.2.1]. Thus, the products were
the same in all samples. On comparing areas under the peaks for
Peak No.2 and Peak No.3 , Peak No. 2 was smaller than Peak
No.3 and with increasing the time Peak No.2 decreased while
Peak No.3 increased [Table 5.2.2]. The ratio between them was
2:6. As a result, Peak No.2 contained two ethoxy groups while
Peak No.3 contained six ethoxy groups. Peak No.2 was tin(II)
ethoxide [Sn(OC2H5)2 ] and stand as intermediate where as,
Peak No.3 might be hexaethoxytin Sn(OC2H5)6 or an oligomer
ditinnoxane [(OC2H5)3Sn-O-Sn(OC *H )3] which stand as the
main product.
After nine hours Peak No.4 was appeared with high
retention time to give another shape of tin ethoxide. The long
time of reaction polymerized tin ethoxide to give a polymer with
high number of ethoxy groups ditinnoxane [(OC2H5)nSn-O-
Sn(OCJi
101
The solubility of the experiments A & B gave the similar
results (See Table 4.4.2). Tin ethoxide dissolved in ethanol and
water then polymerized, the acid and base were good media for
polymerizing tin ethoxide, they were slightly soluble in a non-
polar solvents . The melting point of tin ethoxide in good
agreement with the reported literature (Table 1.5.) , was
unmeltable until 340 °C (See 4.5).
By comparing between experiments A and B, although they had
the similar amounts of starting materials , but they had different
amount of product (Table 4.8.1 to Table 4.8.4). The difference
was ascribed to the change in variables time , speed of stirring
and temperature. The percentage of the product was increased
with increasing the above variables . The difference in the
volume of ethanol was due to the large amount of it was
contributed in the formation of the ethoxides and small amount
was lost as vapour during the filtration and distillation.
102
Table 5.2.1. The Retention Time of the Peaks of Samples of the
Reaction between Stannic Chloride and Ethanol.
103
5.3 ^he^Reftbtion between Sodium Ethoxide and Stannic
CKtorftfe in the presence of Ethanol
104
995 cm"1 due to the formation of tin ethoxide also there was
small peak for (Na-O) ascribed to existence of unreacted sodium
ethoxide .The growth of the tin ethoxide was followed on
increasing time at the range 845-1250 cm-1 [See Fig 4.3.3.4]. A
sample from the first part ^preparation of sodium ethoxide, was
analyzed with GLC. The GLC chromatogram gave two peaks
[Fig.4.3.5 & Fig.4.3.6] and [Table 4.3.4]. Peak No.l was
attributed to the solvent ethanol according to the reference [Fig.
4.3.6]. Peak No.2 had the same retention time like that of
sodium ethoxide . Peak No.3 was due to the product tin(II)
ethoxide [Sn(OC2H5)2 ] and PeakNo.4 was due to hexaethoxytin
Sn(OC2H5)6 or an oligomer ditinnoxane [(OC2H5)3Sn-O-
Sn(OC2H5)3] . Peak No.5 appeared in the product due to the
formation of a polymer [Fig. 4.3.6] .The experiment with the
two parts was repeated. The final product in each had the same
solubility (See Table 4.4.5). The product was soluble in ethanol
and distilled water then polymerized. The product reacted with
acids and bases and it was endothermic . That meant it was not
only one product but also there was others.
105
According to the literature (Table 1.5) a complex of a
double alkoxide of NaSn2(OC2H5)9 was formed so the reaction
was occurred as follows :
A
NaSn2(OC2H5)9+HCl •NaCl + 2 Sn(OC2H5)4 +
C2H5OH
106
Table 5.3.1. The Retention Time of the Peaks of Samples of the
Reaction between Stannic Chloride and Sodium
Ethoxide in the Presence of Ethanol.
107
5.3. Comparison between Tin Ethoxides Produced by the
three Different Methods:
108
Peak No, £ appeared in product of experiment (3.3.3.) due
to a complex NaSn2(OEt)9. An oligomer of experiment (3.3.1)
showed high area under the peak comparing with that of
experiment (3.3.2) and (3.3.3.). The tin(II) ethoxide and the
oligomer of experiments (3.3.2) and (3.3.3.) transferred to
polymers which had the highest area under the peak (Table
3.4.2). Products of (3.3.1) and (3.3.2) containing oligomer of tin
ethoxide while the product of (3.3.3.) containing other products
with tin ethoxide.
109
Table 5.4.1. Comparison of Retention Time (RT) of
Tin Ethoxides Produced by different methods
Area %
Product Peak Peak Peak Peak Peak
No.l No.2 No.3 No.4 No. 5
PI 91.396 1.916 6.385
PI 91.486 1.048 1.906 5.560 —
P3 89.844 0.360 0.120 6.850 2.826
Product Percentage
(%)
PI 1-7.15 Less than 10%
P2 37-41.03 Less than 50%
P3 54.85 - 55.92 More than 50%
110
Conclusion:
HZ
(11) Coates G.E., Creen M.L, Wade K.,Organicmetallic
Compounds, Melthun and Colted London, 3rd ed. Vol (1)
(1967),P:413. \
IIS
(22) Kolthoft I.M. and Elving P.J., Treatise on Analytical
Chemistry part 2, copy right (c)by Interscience publish
Inc., vol. 3, 1961.
(23)Smith A.L., Analysis of Silicons, Wiley London (1974).
114-
(33) Kleinberg, Angersinger and Griswold , Inorganic
Chemistry, D.C, Health and Company, 1st ed, 1960
P:370.