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The Action of Citric Acid and Its Salts in Sugar Solutions PDF
The Action of Citric Acid and Its Salts in Sugar Solutions PDF
The Action of Citric Acid and Its Salts in Sugar Solutions PDF
1929
Recommended Citation
Toulouse, Julian Harrison, "The action of citric acid and its salts in sugar solutions" (1929). Retrospective Theses and Dissertations.
14686.
http://lib.dr.iastate.edu/rtd/14686
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UMI'
THE ACTION OP CITRIC ACID AND ITS SALTS
IN SUGm SOLUTIONS
by
DOCTOft OP PHELOSOPHT
xApproved:
1929
UMI Number: DP14555
UMI
UMI Microform DP14555
Copyright 2006 by ProQuest Information and Learning Company.
All rights reserved. This microform edition is protected against
unauthorized copying under Title 17, United States Code.
TABLE OF C0HT15NTS
Table of contents . ,2
Acknowledgement . 4
Historical . . . . . . . . 14
sugar
beverages 25
Experimental
Purpose , , ,27
Yeast ......29
Results . . . . 3 5
on various syrups 36
^ yeast
The effect of salts on taste ••••••«• 97
oontaminated sugar • • 97
Biscussion 105
Sunme.ry 112
Conclusion • . • . 113
Appendix
The writer wishes to express
IH SUGAR SOLUTIONS
IHTRODUCTIOU
or other micro-organisms.
difficulty.
products.
syrup fall into three classes: the dry mix, the cold process,
amount of water is added and the final syrup made. The dry
experimental part.
just described:-
9
sterile.
one fact stands out. Over a period of six years, and from the
that simple syrup {made from sugar and water alone) may be found
the same syrup with added flavor, acid, and color, shows a marked
syrup are on the same line with the results for the correspond
ing simple syrup made from the same sugar. The samples of
both kinds of syrup were examined after seven to ten days fol
TABLli] I
gravity ^ ;
Simple Syrup Flavored Syrup
100.000 0 1.79
25.000 1.283 «• 4m
44 1.280 2.12
11
ance is made for the fact that a dilution of from one part
TABLr^ II
beveDrages show that the flavored syrup has been made with
little or no acid.
TABLS III
from them
HISTORICAL
made.
Two limits were found: one t he acidity of the medium, and the
that could not stand an acidity of more than 3.3, and others
Others showed some degree of growth over the whole range over
most cases was betv/een 4.3 and 5.9. Peterson (9) (10) also
reports some work with acid and high heat, but no values for
this syrup was less than two minutes. . The same syrup with
Turner, Svanberg (15) finds the optimum range for bottom yeast
concentration was not the only factor but that other character
especially noted:
another the/fact that p«H was not the sole limiting factor in
ion was the same in all solutions after ferraentation had ceased.
almost inert insofar as their killing power for yeast was con
was the first member, and in which sodium hydroxide with the
ide wss calculated from the mass law, there seemed to be a con
and the time necessary to kill 99.9^ of the yeast in the initial
acid has been studied for sometime. There has "been a great
concept to be in error.
net result, if the acid be weak enough, is that the total activ
HHTOg and 0»5 mol cane sugar are dissolved in 1000 grains of
velocity coefficient;-
HCl 10 10 13 19 22
HHO, 5 7 8 1 18
the formation of the weak acid and salt of the strong acid
made for the presence of salts (42). The poorer grades are
concentration.
dealing with the effect of acids with and without the addition
of this, the fact that IT^ ion concentration alone does not
was begun, with the plan of recording those changes in the rate
25
from which they were made. Owen and Kopeloff (loq. cit.)
equipment. r'^^c-s
carrot agar.
than that of Turner. The work of Peterson has also been men
SXPSRIMHirTAL
A. Purpose
nearly 65^ sugar. Most of the beverages based upon this syrup
are made by adding one fluid ounce of fifty percent citric acid
a, 24° Be syrup
0. 30° Be syrup
d. 33° Be syrup
e• 36° Be syrup
B» Source of Materials
a. The yeast
Turner, follows.
was:-
raffinose.
2. Shape, oval
by them.
change in the organism took place over the time of the ex
ture was used. At the end of this time the yeast were well
developed and there were always between six and ten million
yeast would form, and a great many yeasts in spore form could
to densities of 24, 27, 30, 33, and 36° Baurae with distilled
of distilled water. Since the mixture did not "set up" well,
and v?ater were added, with allowance for the salt and acid
the acid and salt solutions were added and well mixed with
flask was well shaken and one c.c. removed for dilution pur
D* Results
used were 0.02, 0.04, and 0.08 1£. Per each acid concen
ent comMnations of acid and salt for each acid level of each
1. Citric acid.
TABIS IV
Citric acid.
Solution number 1 2 3
t
12 hours
Percent survivors
TABLE V
Solution number 45 6
t
Count at end of
Percent survivors
TABLE VI
Solution number 7 8 9
f
Molarity of acid 0.02 0.04 0.08
Count after
492,000 378,000 326,000
3 days
12 » 714,000 432,000
Percent survivors
12 »• 382 235
TABLE Yll
Solution number 10 11
Molarity of acid 0.02 0.04 0.08
Molarity of salt 0.04 0.08 0,16
Original count 188,000 188.000 188,000
Count after
Percent survivors
TABLE VIII
citric acid.
acid
Count after
Percent survivors
^ 2.0 ,752
TABLE IX
Solution number 16 1? ^8
Count after
Percent survivors
TABLE X
Solution number 19 20 21
Count after
Percent survivors
TABLE XI
Solution number 22 23 24
Count after
Percent survivors
TABLE XII
citric acid.
Solution number 25 26 27
J
Molarity of acid 0.02 0.04 0.08
Count after
24 " 30 20
34 » 5 -
Percent survivors
34 " .007
45
TA3L13 XIII
Solution number 28 29 30
4 hours 19,600
8 " 12,300 8,200 2,500
12 '• 640
16 » 550 200 m
24 » 80 20 22
34 " 25
Percent survivors
4 hours 28.8
a •» 18.2 12 .1 3.68
12 » .94
16 « .81 .294
TABLE XIV
Solution number 31 32 33
Count after
16 " - - 200
24 " 70 120 60
34 " 25
Percent survivors
16 " , - - .294
34 " .037
47
TABLE XV
0
36 Be. Syrup with citric acid and sodium
Solution number 34 35 36
Count after
24 " 52 60 12
34 " 12 10
Percent susrvivors
34 " .018
48
Plate 1.
) .
'
Solutions 1, 2, and 3,
49
.Plate 2.
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<£
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Plate 4.
+.5
>4
-/
Plate 5.
t
<2.
X. I
I, 13
14
+4
£o
<{:
'
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-/
53
Plate 6.
iT ^—-—5
t
' 13
6 da vs 12 days 18 davs
Plate 7.
17
23
14
6 dkvs dava
Plate 8
18
15
6 day Si
Plate 9.
'\
i v ' : ^f :••'
\' A r ^ t r
s>
<2
's- 5:S >
W * " ^
' i j ••
• •, .1. . ,MC.,.K.J'.'v . 1 'fvv.n
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? "sr .,;'VA5i-y-,' ^:'';
1 "
J .r
(- i - ^ S ,
• .i:;.-/../'i-*/.
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v/^ 25
u •" / ^ rV'i •"'^
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{ '' ^ ^ ?v
llilllliSMiill 2^
p
16
" 4 I ours ^, '8 ]i()urs ' ,'.12 h0 urs ,;h uT J
Plate 10.
fiiillll#
Plate 11.
f '
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+*
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i:
f ' Y•
? ^ 32
XI
-/
35
I
.26 \
^ 29
8 h)ur8 1$ higwrs
Plate 13,
''•J ," • V
. 13 , -30 Be.'
i 'v '
' ••• ••
N!^25 36°Be.
Plate 14.
•; -
f '
Vc/ \ 2 2?'^
14 30 Be." •
^ 26 36°Be.
i •• • • . •
• 8 h )urs _ : 16 hoiira 24
Plate 15.
t t
\ •
•f*
Q)
s \a \
3 24°Be. ^
15 30°Be.
?
>4
-/
t:^7 36°Be. •
The next series was with 30° Be. syrup alone. The
work of the first series for syrup of this strength was re
peated in part, but with the a-ddition of one other acid con~
TABLI5 XVI
Solution number 37 38 39 40
Molarity of acid 0.01 0.02 0.04 0.08
Original count 63,000 63,000 63,000 63,000
Count after
Percent survivors
TABLE XVII
Solution.number 41 42 43 44
Molarity of acid 0.01 0.02 0.04 0.08
Molarity of salt 0.00250 0.0050 0.01 0.02
Percent survivors
TABLE XVIII
30^ Be. Syrup with citric acid and aodium citrate
Solution number 45 46 47 48
Molarity of acid 0.01 0.02 0.04 0.08
Percent survivors
TABUS XIX
30° Be. Syrup with citric acid and sodium citrate
Solution number 49 50 51 52
Molarity of acid 0.01 0.02 0.04 0.08
Molarity of salt 0.01 0.02 0.04 0.08
Original count 210,000 210,000 186,000 186,000
Coimt after
Percent survivors
TABLE XX
Solution nurafeer 53 54 55 56
Molarity of acid e.ai 0.02 0.04 0.08
Molarity of salt 0.02 0.04 0.08 0.16
Original count 186,000 186,000 186,000 186,000
Count after
Percent survivors
TABLE XXI
Solution number 57 58 59 60
Count after
1 day 417.000 tm
- -
2 « 620,000 - - 39,600
4 « 839,000 45,000 51,300
21 •• 3,200,000 453 22 0
Percent survivors
1 day 179 • -
2 » 267 - 16.9
TABLE XXII
Solution number
61 62 63 64 65 66
Molarity of salt
0.0025 0.010 0.02 0.04 0.08 0.16
Original coimt
226,000 226,000 226,000 226,000 226,000 226,000
Percent survivors
After 4 days
987 668 538 181.4 25.7 15.3
After 10 days
L.84d 1,506 1,762 330 6.37 2.69
After 16 days
1^904 1,966 1,266 663 1.61 .236
After 21 days
734 1,806 1,239 540 .115 .005
70
TABLE XXIII
Solution nura'ber 67 68
10 '• 5,930,000
16 « 4,876,000
21 4,080,000 4,924,000
Percent survivors
4 1,695 1,382
6 1,688 1,554
10 2,816
16 2,080
21 1,944 2,104
Plate 16.
^^
Control
/
/
/
/
/
t
<2
<5
I,
V.
\ >>. 37
.
14
u 39 —
\ i
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f
Plate 17,
53
[45
49
37
^ Plate 18.
50
46
42
58
38
Plate 19,
•9
51
43
+.5
:2J
55
X
1/
f*
So
i!
i:
39
? !l5.59
XI
-/
5 dave
Plate 20.
s.
/
56^v.
-40
Plate 21.
Oontrol
Table XVI.
TABLE XXIV
Solution number 69 70 71
Count after
16 " 235 62 17
20 " 117 3 0
24 " 40 0
Percent survivors
2 0 . 0 9 0
24 " .0308
78
TABLE XXV
Solution number 72 73 74
Percent survivors
TABL^ XXVI
Solution number 75 76 77
Count after
4 hours 5,964
8 « 6,430 2,900 1,246
24 " 140
Percent survivors
4 hours 4.58
16 » .478 .0269
24 " .0108
80
TABLltl XXVII
Solution number 78 79 80
Count after
18 m 1,424 82
21 H 142
Percent isurvivors
18 It .464 .0268
21 II .046
81
TABLE XXVIII
Solution niiraber 81 82 83
21 n
196
24 n
14
Percent survivors
21 II
.0874
24 11
.0062
82
TABLE XXIX
30° Be. Syrup with citric acid and sodium di-
Solution number 84 85 86
9 tf
54,a00 20,800 18,500
12 tt
14,440 7,660 2,308
II
15 5,680 600 260
H
18 1,820 70
11
21 214 14
It
24 66
Percent survivors
6 rt
51.7 33.2 27.2
9 II
26.4 10.1 8.97
II
12 6.98 3.71 1.36
11
15 2.76 .291 .126
18 n .882 .034
II
21 .104 .0068
It
24 .032
83
TABL73 XXX
Solution number 87 88 89
Molarity of acid 0.02 0.04 0.08
Molarity of salt 0.016 0.032 0.0640
Original count 206,000 206,000 206,000
Count after
Percent survivors
TABLR XXXI
TABI® XXXII
Solution number 93 94
Count after
percent survivors
1 hour 98 109.4
Plate 22.
X w
\^ \ \\
69 " 72
Plate 25.
<2
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\ \S
N. \\
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S 0
d» -vV I 8^
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<£ ^ ^ 88
5\ .
: >&76
^ • 'V-
?
.>4,
i'fl "
>\ ^
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full lines • 7 day cultu re \
dash lines • 2 day cultu re \
%o
^ • •• -J: ^... .
Plate 24
:V 1
\\
I, "
w
\v
• •••V- •
J \c^\
• , \
-f* ^ \vv\
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<£. i
k.,
? V
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-^i.f
J 1 " "77 \ NX v9
^ 1 ^ \V83
^ 80
^ ^ 74
;-v;r
TABLE XXXIII
Solution number 95 96 97
12 rt 26,300
13 9,150 6,240
25 " 820
30 '• 137
Percent survivors
10 " 8.82
12 •• 9.0
TABLE XXXIV
10 « m 40,400 47,600
12 '• 27,200 - -
13 « - 13,925 10,831
25 " 708
30 « 158
Percent survivors
10 » - 13.8 16.S
12 " 9.3 -
16 - .57 .339
25 " .242
30 " .054
91
TABLE XXX7
10 - 69,500 55,600
12 »• 36,000 - -
16 « wm 1,656 1,697
25 920
30 " 220
Percent survivors
12.3 m - -
12 "
13 « - 4.19 4.55
16 •• - .567 .58
25 " .314
30 » .075
92
TABLE XXXVI
o
27 Be. Syrup with citric acid and sodium di-
10 n - 110,000 54,200
12 (t 37,000 -
13 « - 18,500 13,962
16 H m 2,247 1,652
25 II 1,208
30 H 197
percent survivors
10 II - 37.7 18.6
II
12 12.7 - -
II
13 m 6.33 4.78
16 It
- .77 .567
II
18 1.61 .298 .055
25 U
.412
30 tt .0675
93
IJABLE XXXVII
48 * 672,000 598,000
Percent survivors
25 •* 204.8 373
48 » 764. 798
94
Plate 25.
£l
<i 2
J
104
xOl 9
Plate 26»
0\
\^\\
A \\
105
102
Plate li't *
< 1
V.
,
"f*
i:
QJ
I!
(i:
?
>4
-/
1\ 106
103
,
< 97
ready dealt with* The sugar used in these runs was heavily
using*
mined*
content was used, and where high salt content as well as high
acid was used, there was little difference between the two
all cases the added salt gave an astringency not found in the
in table XL.
98
TABIE XXXVIII
18 400 1260 - -
36 « 70 482 58 14C
46 •• 44 15 -
60 " 8 142 37
Percent survivors
46 « .496 - .196 -
TABLE XXXIX
^o
30 Be* syrup, with added citric acid and
table XXXVIII.
Solution number
113 114 115 116 117 118
Molarity of acid
0.02 0.02 0.04 0.04 0.08 0.08
Molarity of salt
0.0 0.04 0.0 0.08 0.0 0.16
Original count
Percent survivors
After 20 hours
3.56 17.9 2.27 12.64 1.81 8.63
After 32 hours
.246 1.42 ,08 .80 .053 .445
After 44 hours
•64 .105
After 56 hours
.2S3
100
TABLS XL
and conductivity.
Plate 28
2.4
/
/ 1
1
1
1
/ /
/
i ' i
7 1 1
/ ' '
/ ' '
i 1
'lie*
/JBO° Be •
1
36° Be.
Plate 29.
alt
^— ratio 5:4
d £ alt
CL • O
ra t X 0 0--T3-
^^,,,,-^cid salt
ratio 5:1
r-
105
Discussion
phase, has a marked effect on the shape and slope of the curve
0f02, 0f04, and 0.08 molar citric acid and corresponded to the
was for each acid strength of each syrup density, one solution
show deaths which can "be explained as due to the high concen
be shown by the fact that its range of acidity was that of the
In passing, from 24° to 30° Baume the time is more than halved
o 0
without change of acid strength. In passing from 30 to 36
and death time does not hold. The time by which sterilization
affects of heat.
minimum.
pll 1*'' snd 2»4* At pH 2*05 for example* the killing times
are 13.6 hours for 36° Baume syrup, 16.4 hours for 30° Baume
since the line for 36° Baume syrup crosses through the curve
and not due to experimental error may "be gathered from cer
the water present, they enter into competition for the water.
will he that the organism will not be killed, "but will re
main dormant*
in the appendix.
alone.
was quite close fpH2) to the optimum reaction for the yeast
might have but little effect in the latter case and more
*
in the former.
SUMMARY
acid'concentration#
tion increases.
113
CONCLUSION
syrup is added.
citric acid solution per gallon, seven days; with two ounces
per gallon, five days; and with four ounces per gallon,
thirty hours.
114
1. Buchanan, J« H.
The sugar content of carbonated beverages.
A report to the American Bottlers of Carbonated
Beverages. Unpublished.
2. Owen, L.
The deterioration of cane sugars in storage.
Louisiana Agr. T^xpt. Sta. Bui. no. 162, 1918.
3. Owen, '.V. L.
Bacteriological investigations of sugar cane
products.
Louisiana Agr. ^''.xpt. Sta. Bui. no. 146, 1914.
4. Owen, W. L. ^ r. v,
A study of the deterioration of samples of Cuban
sugars in storage.
Louisiana Planter and Sugar ftianufacturer,
Search 22-29, 1924.
7. McJCelvey, C.
notes on yeast in carbonated beverages.
J. Bact. ja, 98, 1926.
8. Turner, \V. R.
Yeasts from carbonated beverages.
M. S. thesis. Unpublished. lovva State College
Librfiry, Ames, lov/a. 1925.
13. Kolthoff, I. M.
The significance of pH in bacteriology.
Tydschr. vergl. Oenuukunde 11, 268-77, 1925.
14. Weldin, J. C.
The effect of reaction on the growth of yeasts.
(An- abstract)
Proc. Iowa Acad. Sci., 32, 95, 1925.
16. Somogye, E.
The action of acids on yeast fermentation.
Biochem. 2., 120. 100-2, 1921.
18. Rosenblatt, M*
Influence of acids and alcoholic fermentation.
Bulletin Soc. Chim., JL3, 294-9, 1914.
27. Br"onBted, J. K*
Influence of salts on chemical equilibrum in
solutions.
J". Chem. Soc., Loh., 119. 574-92, 19iil.
30. Kolthoff, I»
The hydration of. disaolved sucrose and the
e'xpresaion of the concentration Toy
measuring the activity of the ions.
Verelag* i^kad* Wetenschappen Amsterdam,
281-95, 1926.
31. Scatchard, S.
Speed of reaction in concentrated solutions
and the mechanism of the inversion
of sucrose.
J. AM. Chem. Soc., 4^, 2387-240G, 1921.
33. Clalrk, R. H.
A further investigation of the velocity of
sugar hydrolysis.
J. Am. Chem. Soc., 43, 1759-64, 1921.
38. Taylor, H. S.
The influence of tempertiture in acid catalysis.
J. Am. Chem. Soc., 551, 1915.
43. Clax'k, A.
The influenoe of certain chemicals on the rate
. of reproduction of yeast in wort.
J. Phys. Chem., 221-31, 1924,.
45. Upson, F.
iJome chemical and bacteriological problems in the
soda water industry.
Beverage Journal, 57. no. 2, 59-61, 1921.
Appendix A
sucrose-citric acid-water.
Appendix B
.
O
Appendix C
Appendix D
Citric acid
Mg Ci'trate
0.03 22.1 63.7 95.4
0.06 38.3 75.6 97.5
.
o
to
53211 Citrate
0 0 ale?'
0 ,49 3.21
0 0 3.76
123
Appendix B
1.5 4.05
1.0 3.44 7.64
.6 4.13
.5 1.75
.4 3.52 7.635
.37 2.54
.3 4.22
.24 4.24
.2 1.91 3.60 7.63
.16 3.61 7.625
.15 2.64
.12 4.32
.1 2.06
.08 2,12 3.66
.075 2.69