Professional Documents
Culture Documents
1966
Recommended Citation
Morales, Raul, "A Study on the Precipitation of Calcium as Calcium-Fluoride." (1966). LSU Historical Dissertations and Theses. 1132.
https://digitalcommons.lsu.edu/gradschool_disstheses/1132
This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in
LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact
gradetd@lsu.edu.
This dissertation h as b een
microfilm ed exactly as receiv ed Q6—645 2
M O R A L E S , Raul, 1935-
A S T U D Y O N T H E PRECIPITATION OF
C A L C I U M AS CAL C I U M FLUORIDE.
A Dissertation
in
by
Raul Morales
B.S., University of Southwestern Louisiana, 1961
January, 1966
ACKNOWLEDGEMENT S
granted him.
TABLE OF CONTENTS
PAGE
ACKNOWLEDGEMENT S ii
LIST OF TABLES............................................. v
ABSTRACT.................................................... viii
CHAPTER
I. INTRODUCTION.................................... 1
I I . PRECIPITATION .................................. 9
A. Introduction.............................. 9
A. Introduction. . . . . . . . . . . . . . 36
B. The o r y ....................................... 3 7
C. A p p a r a t u s .................................. 40
V. EXPERIMENTAL RESULTS.............................. 4 4
A. A p p a r a t u s .................................. 4 4
B. S o l u t i o n s .................................. 44
CHAPTER PAGE
F. I n t e r f e r e n c e s ......................... 61
A. Discussion of R e s u l t s ................ 80
B. C o n c l u s i o n s ........................... 83
V I T A ........................................................ 92
iv
LIST OF TABLES
Page
Table
I Suitable Anions Used for Urea Precipi
tations ........................................27
v
Table Page
vi
LIST OF FIGURES
Figure PAGE
vii
ABSTRACT
by conventional procedures.
cium, i.e.,
1) co(nh 2 ) 2 + h 2o = co 2 + 2NH3
2) BF4“ + H 20 = B F 3 (OH)“ + HF
vi ii
of precipitation are discussed. The recommended procedure
ix
CHAPTER I
INTRODUCTION
treated as such.
1
2
and soils that are in contact with the water. Its concentra
tion in fresh water may vary from less than 10 parts per
million (33) .
a concentrated solution.
water.
have shown that cows with high milk production have a posi
tive calcium balance and those with low milk production have
calcium (24).
both very hygroscopic and the latter has the added disadvan
cium because:
PRECIPITATION
A. INTRODUCTION
9
10
cedure .
B. THEORY
gravimetric work.
>
The manner in which nuclei are created is not defi
may be written
0 - - AG/An = - p (2.2)
12
anywhere else.
surface free energy per unit area of surface. But for nuclei
and probably the surface tension will depend on the size re
or molecules in a crystal).
«0
found by letting d ^ G / d n = 0 ,
n = n* = (2^/30)3 (2.4)
it follows from
(2.5)
dissolve completely.
and practice two of which are the fine works of Nielsen (32)
solubility
V (2.7)
where
V = velocity of precipitation
k «* proportionality constant
tion (PFHS).
tate .
conditions of precipitation.
internal pressure.
D
0 a q ] QAcrysta^ (2.9)
law.
23
and Kracek (19), Wahl and Bonner (38) and others to express
D - (Ra/Ba)crystal
(Ra/Ba)solution (2.11)
rewrites eq. (2 .1 0 ) as
dB = X(Brt ~ B)/V
dA (Ac) - A)/V (2.13)
filtrate. The more the values of D and X vary from unity, the
substance.
25
100
80
u 60
1-1
p.
1-
*
<J
0)
a
o
o 40
4J
1-1
3
M*
I 20
has been known for quite some time and, in fact, was employed
the aluminum ion (44). The success of the urea method was
TABLE I
Aluminum Benzoate
Gallium Sulfate
Iron Formate
Thorium Formate
Tin Sulfate
Titanium Sulfate
Zirconium Succinate
and others (4, 5, 6 , 13, 14, 45, 46). These anions can be
below:
and the release of barium and zinc from their complexes with
Haberman and Gordon (17) disagree with this and base their
opinion on the work done by Klein and others. They say that
misnomer.
CHAPTER III
me thods.
30
31
discussed.
ox a l a t e.
(9) .
determination may give high values for the metal when sodium
oxalate, dissolve the precipitate with acid and make the sub
and 622 mp or the line at 422.7 it^p can be used for making
measurements.
212 mp.
A. INTRODUCTION
36
37
B. THEORY
I = Io e " K i) 1 (4.1)
where
(4.2)
where,
e = electronic charge
m electronic mass
c = light velocity
3
N = number of atoms per cm which can absorb in
the range \) to * 0 + d\>
method.
C. APPARATUS
trophotometer include:
(b) atomizer
41
equipment
source.
cn— — (a)---A-— ~L 3
Source Chopper Atomizer \ Selector Detector
cathode lamps are the most useful and most often used sources
b) Atomizer
c) Wavelength Selector
currents to be used.
CHAPTER V
EXPERIMENTAL RESULTS
A. APPARATUS
and that for hydrogen 18 l./min. The aspiration rate for the
sample ws 4 ml./min.
measurements.
B. SOLUTIONS
44
45
ethylene b o t t l e s .
600 ml. of water. The acid was then dissolved with 50%
tainers.
2. Calcium
3. Magnesium
as the indicator.
4. Lead
5. Barium
250 ml.
6 . Sodium
7. Miscellaneous Reagents
8 . Wash Solution
purpo ses.
pH 9-10 and thus remove the turbidity. The samples were then
CH*COO
N-CHjCOO
v CHjCOO
The precipitates obtained in this manner, however, were
produced.
precipitate that was not gelatinous and one which did not
dually .
TABLE II
7 1 .8 4.1-4. 6 -0 .0030
9 1 .8 4.1-4. 6 -0.0015
10 1.9 4.6-5.0 -0 . 0 0 1 1
ranging from 2.0 to 8.0g were used. Upon the slightest sign
heating the solutions with the hot plate set at low (60°c.)
were seen. With the hot plate set on medium (8 8 °C.) the time
15-20 minutes.
further.
was about three hours. At 97°C., the time interval was two
hours. This result plus the fact that the other reaction
cated that it did not matter what anion was associated with
mended procedure.
Table IV.
mended procedure.
TABLE III
Time of
standing^ Calcium obtained(g) Ca in filtrate 5 (g)
0.1975 0.0013
0.1965 0.0019
1 hr 0.1985 0 .0003
0.1980 0.0008
0.1986 0.0006
0.1996 0.0000
0.1992 0.0001
0.1997 0.0000
0.1994 0.0000
0.2001 0.0000
0.1997 0.0002
^Aged at 20°c.
^Time of hydrolysis is 2 hours
C
JBy atomic absorption
TABLE IV
0.1992
0.1994
0.1985
0.1992
0.2004
0.1995
0.1995
0.2000
0.1994
R e p r e s e n t a t i v e values
59
TABLE V
0•
r-~
form.
F. INTERFERENCES
TABLE VI
at Various Concentrations
Ca (ppm) O.D. A B c
50 0.359 -
63
Ca Calibration Curve
Ca and 50 ppm F-
Ca and 100 ppm F~
0'2>
Ca + 100 ppm F-
+ 2 ml H C 1 0 .
OilXt
X illustrate this.
G. RECOMMENDED PROCEDURE
TABLE VII
TABLE IX
TABLE X
TABLE XI
TABLE XII
TABLE XIII
9
1 .5 m l . of fluoboric acid added.
72
is not hygroscopic.
the crystals.
TABLE XIV
Quantities of Calcium Expressed As
10
ltI I ,and III refer to the calcium fluoride expected respectively
from 0.0999g, 0.1998g and 0.2498g calcium added.
74
TABLE XV
Time Weight
0 0.3898
1 hr. 0.3898
4 hrs. 0.3898
8 hrs. 0.3899
1 day 0.3898
2 days 0.3898
5 days 0.3898
7 days 0.3899
11
Initial weight
75
A. DISCUSSION OF RESULTS
sufficiently diminished.
for the filtration; however, most of the work was carried out
may be formulated as
(6 .1 )
82
travel through the burner. Why 60% HClO^ should give the
B. CONCLUSIONS
fluoride, this seems to be the first time that the same method
the oxalate method, since they form quite stable fluoro com
plexes .
a) CO(NH 2 ) 2 + H 2 0 = C0 2 + NH3
b) BF4~ + H 20 = B F 3 (OtT) + HF
86
be considered so (18).
92
EXAMINATION AND THESIS REPORT
Approved:
E X A M I N I N G COMMITTEE:
~Z7