Effects of Anticaking Agents

and Relative Humidity on the Physical

and Chemical Stability of Powdered Vitamin C
C: Food Chemistry

Rebecca A. Lipasek, Lynne S. Taylor, and Lisa J. Mauer

Abstract: Vitamin C is an essential nutrient that is widely used by the food industry in the powder form for both its
nutritional and functional properties. However, vitamin C is deliquescent, and deliquescence has been linked to physical
and chemical instabilities. Anticaking agents are often added to powder systems to delay or prevent caking, but little is
known about their effect on the chemical stability of powders. In this study, various anticaking agents (calcium phosphate,
calcium silicate, calcium stearate, corn starch, and silicon dioxide) were combined with sodium ascorbate at 2% and 50%
w/w ratios and stored at various relative humidities (23%, 43%, 64%, 75%, 85%, and 98% RHs). Chemical and physical
stability and moisture sorption were monitored over time. Additionally, saturated solution samples were stored at various
pHs to determine the effect of surface pH and dissolution on the vitamin degradation rate. Storage RH, time, and
anticaking agent type and ratio all significantly affected (P < 0.05) moisture sorption and vitamin C stability. Silicon
dioxide and calcium silicate (50% w/w) and calcium stearate (at both ratios) were the only anticaking agents to improve
the physical stability of powdered sodium ascorbate while none of the anticaking agents improved its chemical stability.
However, corn starch and calcium stearate had the least adverse effect on chemical stability. Dissolution rate and pH
were also important factors affecting the chemical and physical stability of the powders. Therefore, monitoring storage
environmental conditions and anticaking agent usage are important for understanding the stability of vitamin C.
Keywords: ascorbic acid, chemical composition, isotherms, particle size distribution, shelf life

Practical Application: Anticaking agent type and ratio significantly affected the physical and chemical stability of vitamin
C over time and over a range of RHs. No anticaking agent improved the chemical stability of the vitamin, and most
caused an increase in chemical degradation even if physical stability was improved. It is possible that anticaking agents
would greatly affect other chemically labile deliquescent ingredients, and therefore, anticaking agent usage and storage
conditions should be monitored in blended powder systems.

Introduction (RH) exceeds the deliquescence RH of the ingredient (RH0 ),

The chemical and physical stability of powder ingredients and
products is important for many industries. Each year, the phar-
maceutical, chemical, and food industries manufacture an average
of 300000 tons of solid product per company (Wahl and others
2008). Moisture may adversely affect the processability as well as
the functionality of these powders, and therefore, understand-
ing and controlling product–moisture interactions is necessary.
The type(s) of solid ingredients in a powder product will in-
fluence the mode of water–solid interaction and stability (Zografi
1988). For deliquescent crystalline ingredients (such as the widely
used ascorbic acid, sodium ascorbate, citric acid, glucose, sucrose,
and sodium chloride), when the environmental relative humidity
MS 20110448 Submitted 4/7/2011, Accepted 6/17/2011. Authors Lipasek and
Mauer are with Dept. of Food Sci., Purdue Univ., West Lafayette, IN 47907,
U.S.A. Author Taylor is with Dept. of Industrial and Physical Pharmacy, Purdue
Univ., West Lafayette, IN 47907, U.S.A. Direct inquiries to author Mauer (E-mail:
mauer@purdue.edu).
the ingredient undergoes a first-order phase transformation from
solid to solution (Zografi 1988; Mauer and Taylor 2010). For-
mulation has been shown to significantly affect moisture sorp-
tion and chemical stability of deliquescent ingredients in powder
blends (Ortiz and others 2009; Hiatt and others 2010b; Mauer
and Taylor 2010). Deliquescence has also been linked to caking
and agglomeration of powder products (Salameh and others 2006).
However, these studies did not include anticaking agents in the
formulations.
Caking is an outcome of a combination of formulation and
storage conditions, including RH, temperature, pressure, compo-
sition, and particle size (Chen and Chou 1993). Anticaking agents
are often added to food systems to improve the physical properties
and stability, and the selection of the anticaking agent is based upon
a wide range of criteria. Anticaking agents have been shown to
compete for moisture, act as a moisture barrier, eliminate surface
friction, or inhibit growth or change of crystal lattice structures
(Peleg and Mannheim 1973; Peleg and Hollenbach 1984; Aguil-
era and others 1995; Barbosa-Canovas and others 2005). Com-
mon anticaking agents include calcium silicate, calcium stearate,
silicon dioxide, tricalcium phosphate, and corn starch (Peleg and

C 2011 Institute of Food Technologists

 R

C1062 Journal of Food Science r Vol. 76, Nr. 7, 2011 doi: 10.1111/j.1750-3841.2011.02333.x
Further reproduction without permission is prohibited
Effect of anticaking agents on vitamin C. . .
Mannheim 1973). Much research has been conducted on the
effect of anticaking agents in regard to the physical stability of
powder blends (Irani and others 1959; Peleg and Mannheim
1973; Chen and Chou 1993; Hansen and others 1998), but these
studies failed to address the chemical stability of the powdered
ingredients.
Vitamin C is an essential nutrient that is often fortified into
foods and beverages and is usually distributed in the powdered
form. It is often added to foods in forms such as ascorbic acid or
sodium ascorbate not only for nutritional value and label claims
but also for stability of the food product (Kranl and others 2005;
Polinati and others 2010). Vitamin C is known to function as
a preservative, antioxidant, color fixing agent, and nutrient (Ash
and Ash 2008). To maintain functionality, vitamin C must be
reasonably stable; however, many studies refer to vitamin C as one
of the most unstable vitamins added to foods (Kampuse and others
2002; Kitao and others 2006; Riaz and others 2009). In order to
prevent moisture-induced physical changes, anticaking agents are
used in many products. However, little information is available on
the effects of anticaking agents on both the physical and chemical
stability of deliquescent ingredients. It was, therefore, of interest to
determine how the addition of anticaking agents to a chemically
labile deliquescent ingredient (vitamin C powder) would influence
its physical and chemical stability across a range of environmental
treatments.
Materials and Methods
Materials
The following anticaking agents were used: calcium silicate
(SIL), calcium stearate (STE), silicon dioxide (DIO), corn starch
(CS), and tri-basic calcium phosphate (PHO). All of the anticak-
ing agents except for corn starch were obtained from Spectrum
Chemical (Newbrunswich, N.J., U.S.A.). Corn starch was ac-
quired from Tate & Lyle (Lafayette, Ind., U.S.A.). Sodium ascor-
bate (ASC) was purchased from Sigma-Aldrich Inc. (St. Louis,
Mo., U.S.A.). The following chemicals were used for the prepa-
ration of samples for the microplate reader chemical stability
analysis: trichloroacetic acid and 2,2-bipyridine (Mallinckrodt-
Baker, Phillipsburg, N.J., U.S.A.); iron chloride and ethanol (EMD
Chemicals, Gibbstown, N.J., U.S.A.); and potassium phosphate
monobasic and dibasic (Mallinckrodt Baker, Paris, Ky., U.S.A.).
Solid sodium hydroxide pellets >98% and hydrochloric acid
(Mallinckrodt-Baker) were utilized to create saturated pH solu-
tions. Saturated solutions of the following salts were used to control
the RH of various desiccators: potassium carbonate, sodium chlo-
ride, potassium chloride, and potassium sulfate (Sigma-Aldrich),
and potassium acetate and copper chloride (Mallinckrodt-
Baker). All pH calibration buffers were purchased from Sigma-
Aldrich.
Methods
Powder preparation and blend mixing. Single ingredients
and binary mixtures of the anticaking agents with ASC were pre-
pared by geometric mixing, and 1-g samples were weighed into
20-mL glass scintillation vials. Geometric mixing, as described by
Salameh and others (2006), was used to create 50:50 and 98:2
w/w blends of ASC with the various anticaking agents. The ratios
of the anticaking agents were chosen to represent FDA regulated
levels (2% w/w) (FDA 2011) and extreme conditions (50% w/w)
for scientific enquiry into the mechanisms of action for each of
the anticaking agents.
Moisture sorption isotherms for individual ingredients and
blends
Individual ingredients. Moisture sorption isotherms for in-
dividual ingredients were generated using a Thermal Gravimet-
ric Analyzer (TGA) Q5000 (TA Instruments, New Castle, Del.,
U.S.A.). ASC samples were analyzed at 25 ◦ C to determine mois-
ture sorption and the deliquescence point (RH0 ) following a
C: Food Chemistry
method described by Salameh and others (2006). Anticaking agent
samples (PHO, SIL, STE, CS, and DIO) were analyzed at 25 ◦ C
to determine moisture sorption profiles. Samples with weights of
5 to 10 mg were dried for 60 min at 60 ◦ C in the TGA. The ASC
samples were analyzed over a RH range of 75% to 92% RH at a
step rate of 1.00%. The anticaking agent samples were analyzed
over a RH range of 10% to 95% RH at a step rate of 5% RH. All
samples were allowed to equilibrate through a criterion of 0.01%
w/w in 5 min or a maximum time of 60 min. Moisture sorption
isotherms were also generated by weighing ingredients through-
out the storage treatments to monitor weight gain over time and
relate this moisture sorption to physical and chemical stability.
Blends. Moisture sorption isotherms for blends of ASC with
anticaking agents at 2% and 50% w/w ratios were generated using a
Symmetrical Gravimetric Analyzer (SGA-100) (VTI Corporation,
Hialeah, Fla., U.S.A.) at 25 ◦ C. Samples of 10 to 15 mg were dried
at 60 ◦ C in the sorption analyzer with an equilibrium criterion of
0.01% w/w in 2 min and a maximum drying time of 60 min. The
samples were analyzed over a range of RHs with an equilibrium
step criterion of 0.01% in 5 min with a maximum step time of
60 min. Samples were analyzed from 20% to 60% RH with a step
rate of 20% RH, from 70% to 80% RH with a step rate of 5% RH,
and from 80% to 92% RH with a step rate of 1% RH. The RH0
of the ASC in the blend was determined from the isotherm as the
RH at which the sample began to rapidly sorb moisture (Salameh
and others 2006). Moisture sorption isotherms were also generated
by weighing ingredient blends throughout the storage treatments
to monitor weight gain over time and relate this moisture sorption
to physical and chemical stability.
Controlled RH storage. Controlled RH chambers at am-
bient temperature (22 ± 3 ◦ C) were prepared using the follow-
ing saturated solutions: potassium acetate (23% RH), potassium
carbonate (43% RH), copper chloride (64% RH), sodium chlo-
ride (75% RH), potassium chloride (85% RH), and potassium
sulfate (98% RH). The RH of each chamber was verified us-
ing a digital hydrometer (Traceable humidity/Temperature/Dew
point meter, Control, Co., Friendswood, Tex., U.S.A.) and a wa-
ter activity meter (Aqualab 3TE, Decagon Devices, Inc., Pullman,
Wash., U.S.A.). Saturated salt solutions for each experimental RH
condition were analyzed after a 24-h storage period to deter-
mine the water activity of the solutions. When the water activity
readings of the solutions and the digital hygrometer readings in
the chambers matched, as water activity is equal to %RH/100
(Tang and Munkelwitz 1993), the RH in the chamber was con-
sidered to be verified. All samples were stored at room temper-
ature (22 ± 3 ◦ C) for exposure to all 6 RH levels for up to
5 wk. At select time intervals, the samples were weighed to deter-
mine weight gain attributable to moisture sorption, and chemical
stability was analyzed immediately after removal from the RH
chambers.
Physical stability. The initial particle sizes of all individual
ingredients and binary mixtures were analyzed in triplicate using a
Mastersizer 2000 particle size analyzer with a Scirocco 2000M(A)
accessory attachment (Malvern Instruments Ltd., Worcester-
shire, U.K.) following the manufacturer’s directions. Both the
Vol. 76, Nr. 7, 2011 r Journal of Food Science C1063
 Effect of anticaking agents on vitamin C. . .
background and the sample were set to measure 5000 snaps every
5 s with a beam length of 10.00 μm. The instrument was set up for
general purpose use with samples size selection of 0.02 to 2000.00
μm and normal sensitivity mode. Obscuration parameters were
set from 1 to 8. Mastersizer 2000 version 5.20 software (Malvern
Instruments Ltd.) was used for data analysis. All of the anticaking
agents had an initial individual particle size much smaller than
C: Food Chemistry
that of the ASC (Table 1). The STE was not analyzed due to
its hydrophobic nature and its tendency to stick to the walls of
the instrument. Following initial characterization, the powdered
samples were stored in triplicate at 75%, 85%, and 98% RH at
ambient temperature (22 ± 3 ◦ C), and the analysis was conducted
on day 0 and at wk 2 and 4. D(0.5) values, the median particle di-
ameter, and D(0.9) values, the particle diameter under which 90%
of the particles are depicted, were determined. Visual observations
of the formation of solid cakes and liquid solutions throughout the
storage treatments were also recorded.
Chemical stability analysis. Treatment effects on vitamin C
chemical stability were measured using a method adapted from
Stevens and others (2006) and Hiatt and others (2010b). Samples
were removed from the desiccators, weighed, and then diluted
with distilled water to a final volume of 100 mL, except for the
50:50 ASC:STE samples which were diluted in a 10% ethanol
solution. Fractions of the dilution (100 μL) were further diluted
in a 6% TCA solution to 1.5 mL and then plated on a 96-well mi-
croplate (Becton, Dickinson and Company, Franklin Lakes, N.J.,
U.S.A.). The vitamin C content remaining was determined using
a UV/VIS AD 340 Microplate Reader (Beckman Coulter, Inc.,
Brea, Calif., U.S.A.) at an absorbance of 570 nm and comparing
results to a standard curve of known ASC concentrations (Stevens
and others 2006; Hiatt and others 2010b).
Saturated solutions of sodium ascorbate. Saturated solu-
tion samples were prepared in triplicate by combining 300 μL of
distilled water per 1 g of ASC in sealed 20-mL glass scintillation
vials. This treatment was previously used to estimate the RH0 of
deliquescent ingredients (Salameh and Taylor 2005). Samples were
stored for up to 5 wk at room temperature (22 ± 3 ◦ C). The satu-
rated solution water activity was determined using a water activity
meter (Aqualab 3TE, Decagon Devices, Inc.). Chemical stability
was monitored over time using the method described above.
pH treatments. To investigate the effects of pH on ASC sta-
bility in saturated solutions, samples were prepared in triplicate by
combining 300 μL of varying ratios of 1 M hydrochloric acid and
1 M sodium hydroxide per 1 g of ASC to reach the desired pHs
(5, 6, 7, 8, or 9). The pH was determined by a pH meter (IQ
150 pH/mV/Thermometer with ISFET sensory probe, IQ Sci-
entific Instrument, Loveland, Colo., U.S.A.) that was calibrated
at pHs 4, 7, and 10. Samples were stored in sealed 20-mL glass
scintillation vials at ambient temperature (22 ± 3 ◦ C). Chemi-
Table 1– Initial particle size analysis for individual ingredients.
Particle size (μm)b
Refractive
Sample indexa D(0.5) value
Calcium phosphate 1.63 12.830 ± 2.632
Calcium silicate 1.63 8.396 ± 0.878
Calcium stearate c c
Corn starch 1.45 14.314 ± 0.019
Silicon dioxide 1.45 15.312 ± 1.038
Sodium ascorbate 1.52 86.549 ± 2.269
a
Parameters utilized for particle size measurements.
b
Particle size data reported are averages of triplicate analyses with standard deviation. icant (P < 0.05) amount of moisture into the system below the
c
Sample not analyzed due to its hydrophobicity and incompatibility with the instrument. RH0 while STE and PHO alone did not (Figure 1A). Thus, an
C1064 Journal of Food Science r Vol. 76, Nr. 7, 2011
cal stability was monitored over time using the method described
above.
Statistical analysis. A completely randomized three-factor
factorial design was used to determine the effects of type and ratio
of anticaking agent, RH, and time on the physical and chemi-
cal stability of the ASC. For physical stability analysis based on
visual observation, blends that formed a solid cake or a liquid
solution were considered to be significantly different from a free
flowing powder. For data on moisture sorption, chemical stability,
and physical stability determined by particle size analysis, ANOVA
models were utilized for the statistical analysis, and individual dif-
ferences were analyzed using least-squares means and Tukey multi-
ple comparisons procedures. The statistical analysis was conducted
using PC SAS 9.2 (SAS Institute Inc., Cary, N.C., U.S.A.) with
α = 0.05.
Results and Discussion
Effects of RH, storage, and anticaking agents on moisture
sorption
The moisture sorption profiles of all individual ingredients used
in this study are shown in Figure 1A. It is evident that there
were distinct differences in moisture sorption between the differ-
ent ingredients. The profile of ASC displaying a sharp increase
in moisture sorption above the deliquescence RH (85.8% to 86%
RH) is consistent with previous reports (Hiatt and others 2010b).
At RHs below the RH0 , deliquescent ingredients sorb only a few
molecular layers of water (Foster and Ewing 2000), while rapid
moisture sorption is observed at RHs above the RH0 (Mauer and
Taylor, 2010). Of the anticaking agents, DIO, CS, and SIL had
sigmoidal sorption isotherms, demonstrating increasing moisture
sorption as RH increased. These anticaking agents sorbed signif-
icantly (P < 0.05) more moisture than ASC at RHs below 86%
RH. PHO did not have a significant increase in moisture sorption
until the RH exceeded 90%, and STE did not significantly gain
weight over the experimental RH range (0 to 95% RH).
Moisture sorption isotherms for all blends of ASC with 2%
and 50% w/w anticaking agent are displayed in Figure 1B and C,
respectively. Formulation significantly (P < 0.05) affected mois-
ture sorption. Although the overall isotherm shape for samples
containing 2% anticaking agent was similar to ASC alone (Fig-
ure 1B), moisture sorption was greater for these blends than for
the ASC at RHs above the ASC RH0 (note the inset in Fig-
ure 1B). Some moisture (less than 2% weight gain) was sorbed at
RHs below the RH0 , while moisture was increasingly sorbed (up
to 58% weight gain for ASC:CS blends) at RHs above RH0 in
all 2% anticaking agent blends. All ASC blends containing 50%
anticaking agent, except for the STE blends, sorbed more mois-
ture than ASC alone before the sharp increase in moisture gain at
the deliquescence point (Figure 1C). At RHs below RH0 , DIO,
CS, and SIL brought more than 5% weight gain into the system.
Blends containing 50% PHO sorbed less moisture than the 50%
blends of DIO, CS, and SIL but more moisture than the blends
D(0.9) value containing 2% PHO at RHs below RH0 . The blends containing
27.953 ± 5.104
50% STE sorbed less moisture than the other 50% anticaking agent
111.288 ± 13.010 blends and followed similar trends to ASC alone and the 2% w/w
c
blends.
20.672 ± 0.0297 These trends are somewhat consistent with the expected be-
94.950 ± 8.178 havior based on the moisture sorption profiles of the individ-
302.883 ± 15.558
ual ingredients: DIO, SIL, and CS individually brought a signif-
Effect of anticaking agents on vitamin C. . .

increase in moisture sorption in ASC blends containing increasing
amounts of DIO, SIL, and CS would be expected at RHs below
RH0 . However, although STE alone did not sorb a noticeable
amount of moisture at RHs up to 95%, blending STE with ASC
did not decrease the moisture sorption compared to ASC alone.
The type and ratio of anticaking agent had a slight effect on the
deliquescence behavior, with the break in the isotherm indica-
blends containing 2% anticaking agent slightly shifted the RH0
of the ASC to a higher RH than the ASC alone (85.8%), up to
88.5% RH for the 98:2 ASC:STE blends. All blends containing
50% anticaking agent, except for STE, did not significantly af-
fect the RH0 of ASC, maintaining an RH0 between 85.5% and
86.4% RH. The 50% STE blend, similar to the 2% STE blend,
had a higher deliquescence RH than the ASC alone. The 50:50

C: Food Chemistry
tive of deliquescence ranging from a low of 85.5% RH for 50:50 ASC:STE exhibited deliquescence behavior at 87.4% RH. Al-
ASC:PHO blends up to 88.5% RH for 98:2 ASC:STE blends. All though increasing concentrations of anticaking agents in blends

Figure 1– (A) Moisture sorption isotherms for sodium

ascorbate and anticaking agents over a range of
relative humidities at 22 ± 3 ◦ C through the use of a
TGA Q5000. Samples indicated as: silicon
dioxide; calcium stearate; calcium
silicate; calcium phosphate; sodium
ascorbate; cornstarch. (B) Moisture sorption
isotherms for sodium ascorbate with and without
anticaking agents at 2% w/w at 22 ± 3 ◦ C through
the use of a VTI SGA-100. Mixtures: silicon
dioxide 2%; calcium stearate 2%;
calcium phosphate 2%; sodium ascorbate
(control); cornstarch 2%; calcium silicate
2%. (C) Moisture sorption isotherms for sodium
ascorbate with and without anticaking agents at
50% w/w at 22 ± 3 ◦ C through the use of a VTI
SGA-100. Mixtures indicated by: silicon dioxide
50%; calcium stearate 50%; calcium
silicate 50%; calcium phosphate 50%;
sodium ascorbate (control); cornstarch 50%.

Vol. 76, Nr. 7, 2011 r Journal of Food Science C1065

 Effect of anticaking agents on vitamin C. . .

with ASC increased the moisture sorption at RHs below the RH0 storage treatments in the dessicators (Figure 2A and B) than in the
compared to ASC alone, the RH0 was not shifted up or down to shorter-term automated gravimetric measurements (Figure 1) for
a great extent by any of the anticaking agents. all samples at RHs above 64% RH. Considering the blends, this
While the moisture sorption isotherms of the ingredients could be an indication that the anticaking agents are less effective
and blends generated using automated gravimetric instruments at delaying moisture sorption over time than they are for repelling
(Figure 1) provide some insight into the behavior of the samples or competing for moisture over a short time (Barbosa-Canovas
over a short time, it was important to monitor the moisture sorp- and others 2005). The ASC alone did not begin to rapidly sorb
C: Food Chemistry

tion profiles of all ingredients and ASC–anticaking agent blends moisture until the RH was above the ASC RH0 , 86% RH, for
over longer storage times at select RHs to correlate moisture sorp- the automated gravimetric analysis, while the ASC alone sorbed
tion to physical and chemical stability of the blends. As expected, a significant amount of moisture (P < 0.05) at 85% RH during
the type of anticaking agent as well as the ASC–anticaking agent the dessicator studies. This may be due in part to the timescale
ratio had a significant effect (P < 0.05) on moisture sorption dur- differences between the instrumental 60-min equilibration time
ing storage. Throughout the storage treatments, limited moisture and the approximately 4-wk duration of the desiccator ex-
sorption occurred at and below 64% RH for all samples (with a periments; however, these differences could also be caused by
maximum of 2.50% ± 0.17% weight gain for 50% w/w CS blends moisture-mediated degradation and the enhanced hygroscopicity
and a minimum of 0.27% ± 0.034% for 2% w/w SIL blends at of resulting degradation products (Hiatt and others 2008; Kwok
64% RH). Formulation significantly affected moisture sorption at and others 2010).
75% RH and above (examples shown in Figure 2A and B). Large To further investigate the observation that the blends of ASC
differences were evident in the moisture sorption profiles over with anticaking agents were sorbing more moisture than the ASC
time at 85% RH of ASC and its blends containing 2% anticaking alone, and to determine if the moisture uptake in the blends
agent (Figure 3), with ASC alone sorbing the least moisture. All was additive or synergistic, data were treated as if the mois-
of the blends containing 2% anticaking agent, except for STE, ture sorption in the blend was only dependent on the amounts
sorbed more moisture than the 50% ratio blends at 75% and 85% of the individual ingredients in the blend and their individ-
RH, while both sorbed more moisture than ASC alone at 75% ual hygroscopic behaviors. These additive data were then com-
and 85% RH. Interestingly, more moisture was sorbed during the pared to the observed moisture sorption patterns (Figure 2C–D).

A 100 C 100
90 90

80 80

70
70
Moisture Sorption (%)

Moisture Sorption (%)

60
60
50
50
40
40
30
30
20
20
10

10
0
20 30 40 50 60 70 80 90 100
Relative Humidity (%)
0
20 30 40 50 60 70 80 90 100
B 100 Relative Humidity (%)

90
D 100
80 90

70 80
Moisture Sorption (%)

60 70
Moisture Sorption (%)

60
50

50
40

40
30
30
20
20
10
10
0
20 30 40 50 60 70 80 90 100 0
Relative Himidity (%) 20 30 40 50 60 70 80 90 100
Relative Humidity (%)

Figure 2– Observed moisture sorption profiles over a range of relative humidities after 32 d at 22 ± 3 ◦ C for single and binary mixtures of sodium
ascorbate with corn starch (A) or silicon dioxide (B) compared to predicted moisture sorption for 98% and 50% ratios w/w of sodium ascorbate with
corn starch (C) or silicon dioxide (D). Single and binary mixtures for sodium ascorbate (ASC) and anticaking agents (AA) are as follows: 100%
sodium ascorbate; 98% ASC: 20% AA; 50% ASC:50% AA; 100% anticaking agent; observed ratio; predicted 2% ratio;
observed 50% ratio; predicted 50% ratio.

C1066 Journal of Food Science r Vol. 76, Nr. 7, 2011

Effect of anticaking agents on vitamin C. . .
Interestingly, all blends at both ratios sorbed significantly more
moisture (P < 0.05) than predicted from the individual ingredients
at 75%, 85%, and 98% RH but not at storage RHs at or below 64%
RH. The observation that blends synergistically sorb moisture is
consistent with previous studies (Ortiz and others 2009; Hiatt and
others 2010a) and is concerning for their chemical and physical
stability.
Effect of storage RH and anticaking agents on ASC
physical stability
The effects of anticaking agents on the physical stability of ASC
were determined over time by observation and monitoring particle
size (Table 2). When comparing formulations, enhanced physical
stability is shown as an increased time to form a solid cake (or
liquid), as well as by minimal or delayed changes in particle size
distribution as compared to the initial product at any given time
point. The data trends are consistent with the multistage process of
caking described by Aguilera and others (1995) in which a powder
system converts from a free flowing powder to a liquid solution.
During the initial stage of bridging, particles form reversible, small
intermolecular interactions with one another. The bridges become
permanent through the next stage of agglomeration, while the
system is still highly porous and continues to absorb environmental
moisture. The next stage of caking is compaction in which the
solid bridges widen as individual particle sizes decrease. Finally,
liquefaction occurs in which the entire sample becomes dissolved
in solution due to the higher moisture content (Aguilera and others
1995). The D(0.9) value for the particle size is a representation of
the largest 10% of the particles; therefore, an increase in the D(0.9)
value represents the increase of caking as particles began to clump
together. This follows the multistep caking mechanism described
by Aguilera and others (1995): the increase in the D(0.9) value is
indicative of the agglomeration step in which permanent bridges
form between particles, increasing the overall size of the particle
and decreasing the overall physical stability.
Overall, storage RH and time had a significant (P < 0.05) effect
on the physical stability of ASC and its blends with anticaking
agents. More samples in the 75% RH chamber remained free
flowing powders after 2 wk than in the 85% RH chamber, and
most samples had liquefied within 3 d of placement in the 98%
RH dessicator. Many of the samples began to convert to a solid
cake and then to a liquid form over time (as reported for the
following samples in Table 2: 2% DIO and 2% SIL at 75% RH,
and CS and PHO at both ratios at 85% RH).
Liquefaction of ASC samples stored at RHs above the RH0
(approximately 86% RH) was expected due to the deliquescence
phenomenon (Figure 1). At RHs below the RH0 , the ASC was
expected to be physically stable because only a few molecular lay-
C: Food Chemistry
ers of moisture are sorbed by deliquescent ingredients below the
RH0 (Foster and Ewing 2000); however, caking was observed in
ASC stored at both 75% and 85% RH. As shown in Table 2,
the increased particle size for ASC alone from wk 0 to wk 2 is
an indication of the formation of the intermolecular interactions
that lead to increased caking and clumping of the sample. At 85%
RH, a solid cake was formed in 2 wk, while at 75% RH, a solid
cake did not form until wk 4. If the ASC had sorbed only a few
molecular layers of water at these RHs (which could have been
likely according to Figure 1), then there may not have been enough
moisture present to form intermolecular interactions leading to the
bridging and agglomeration phases of caking (Aguilera and others
1995). However, an increasing amount of moisture was sorbed
by ASC over time: over the 32 d at 85% RH, the ASC samples
sorbed approximately 5% moisture (Figure 3). For ASC samples
sorbing greater than 0.3% moisture (equivalent to 0.04 mmol of
moisture to 1 mmol of ASC), caking was observed. Although this
would not be expected in pure crystalline samples stored below the
RH0 , impurities present within the powder or moisture-induced
degradation could have led to the observed enhanced hygroscop-
icity, which in turn contributed to the loss of physical stability
(Hiatt and others 2008).
Anticaking agent type and ratio significantly (P < 0.05) affected
the physical stability of the ASC powder blends. The addition of
anticaking agents to ASC either enhanced or reduced physical
stability depending upon the type and ratio (Table 2). Blends
containing 50% DIO or SIL had a greater physical stability than
ASC alone, while blends containing 2% PHO, DIO, or SIL were
less stable than ASC. Blends containing 50% CS were more stable
than ASC alone at 75% RH but less stable than ASC alone at 85%
RH. Blends containing 50% STE appeared to be physically stable at
75% and 85% RH but the particle size analysis of STE-containing
samples could not be completed with the Malvern instrument.
In comparison, the 2% w/w anticaking agent blends were less
Figure 3– The moisture sorption over time for
sodium ascorbate with and without 2% w/w
anticaking agents held at 85% RH at 22 ± 3 ◦ C
for up to 32 d Samples shown as: Sodium
ascorbate; calcium stearate; calcium
phosphate; calcium silicate; silicon
dioxide; cornstarch.
Vol. 76, Nr. 7, 2011 r Journal of Food Science C1067
 Effect of anticaking agents on vitamin C. . .

effective than the 50% blends at preserving physical stability. All
samples with 2% anticaking agent were either solid or liquid at all
RHs (75%, 85%, and 98%) after 2 wk, except for CS and STE at
75% RH. After 4 wk, all 2% anticaking agent samples were solid
or liquid.
According to Adhikari and others (2001), anticaking agents are
only effective at usage levels up to 2% w/w. Irani and others
C: Food Chemistry
it could have pulled moisture away from ASC and prevented the
bridging step of caking. This is consistent with the observation
that blends of SIL sorbed significant amounts of moisture below
the RH0 of ASC (Figure 1) but maintained physical stability longer
than other anticaking agents (Table 2). Silicon dioxide (DIO) was
also effective at maintaining physical stability of the powder blend,
and it has the ability to inhibit caking by preventing surface defor-

(1959) analyzed the effects of anticaking agents on a wide range
of powders, including 2 deliquescent ingredients, and determined
that anticaking agents used at higher ratios were less effective at
preventing caking. Based on the results of this study, the higher
ratio of anticaking agent was more effective at preserving physical
stability of the ASC. However, the 50% ratio blends also sorbed
a greater amount of moisture (Figure 1B and C) than the 2%
blends. Although anticaking agent levels of 50% are not permit-
ted for use in food products, the dramatic difference between the
2 ratios of 2% and 50% w/w indicated that higher levels of an-
ticaking agents may delay caking of deliquescent food powders
but may also bring more moisture into the powder system. Thus,
the amount of moisture is not an independent indicator of loss of
physical stability.
Anticaking agents have been added to other deliquescent food
ingredients to enhance their physical stability. Sodium chloride,
a common deliquescent ingredient with a RH0 of 75% RH, is
regularly combined with anticaking agents (such as PHO, DIO,
sodium ferrocyanide, and sodium aluminum silicate) to inhibit
caking (Hui 2006; Ogur and others 2008). Based on the results
of this study, SIL, DIO, and STE were the most effective an-
ticaking agents at preserving the physical stability of ASC (Ta-
ble 2). Therefore, the most effective anticaking agents to pre-
vent physical changes in ASC blends are not necessarily the ones
that are most commonly used in blends with other deliquescent
ingredients.
The effectiveness of the anticaking agents for maintaining the
physical stability of powder blends is largely due to their specific
mechanisms for caking prevention. SIL was one of the most effec-
tive anticaking agents at enhancing physical stability (Table 2), and
this may be due to its ability to absorb water to specific sites of the
molecule with a high binding energy and absorption of up to 2.5
times its weight in water (Aguilera and others 1995). Therefore,
mation and powder stickiness. This delays the formation of inter-
particle bridges in caking (Peleg and Hollenbach 1984; Aguilera
and others 1995; Barbosa-Canovas and others 2005). This may be
why the physical stability was enhanced (Table 2) although signif-
icant amounts of moisture were sorbed below the RH0 (Figure
1) in ASC-DIO blends. Calcium stearate (STE) acts as a water
repellant due to its hydrophobic nature (noticeable in its lack of
moisture sorption in Figure 1) and acts as a barrier between the
water and host ingredient particles, thereby preventing the ag-
glomeration step of caking (Peleg and Mannheim 1973; Peleg and
Hollenbach 1984). Although the effectiveness of STE could not be
measured using the Malvern instrument, visual observations indi-
cated good stability for the ASC-STE powder blends. The specific
anticaking mechanisms for tricalcium phosphate (PHO) and corn
starch have not yet been reported, but these anticaking agents
are often used in foods due to their low cost and perceived effi-
cacy in the food industry (Peleg and Mannheim 1973). However,
PHO was least effective at preventing caking in the ASC samples
(Table 2).
It has also been proposed that anticaking agents can affect a host
powder by altering intermolecular interactions (Yang and others
2005). Small particles, such as anticaking agents, may adhere to
the surface of a larger rough particle to enhance ordered mixing
and flowability (Hersey 1975). This increased degree of mixing
smoothes the larger particle surface and decreases interactions be-
tween the larger particles. The anticaking agents used in this study
had a smaller particle size than the sodium ascorbate (Table 1).
The differences in particle size distribution for each anticaking
agent (differences between D(0.5) and D(0.9) values in Table 1)
may have led to differences in surface coating and intermolecular
interactions with sodium ascorbate. This in turn may have affected
the physical stability of the sodium ascorbate blends over time at
the various RHs (Table 2).

Table 2–Particle size analysis for single and binary mixtures of sodium ascorbate with anticaking agents stored at various relative humidities
(RH) at 22 ± 3 ◦ C after 0, 2, and 4 wk.
Particle size (μm) at given RH and weekab
75% RH storage 85% RH storage 98% RH storage
cd e
Sample RI Week 0 Week 2 Week 4 Week 2 Week 4 Week 2 Week 4
ASC 100% 1.52 302.883 ± 15.558A 334.365 ± 8.295#B S S S Lf Lf
DIO 2% 1.52 323.612 ± 33.188 S L S L Lf Lf
DIO 50% 1.52 197.087 ± 9.581C 242.455 ± 32.823D 266.578 ± 68.578D 243.578 ± 17.779D 372.889 ± 38.308E S Lf
SIL 2% 1.52 315.120 ± 14.969 S L L L Lf Lf
SIL 50% 1.52 278.033 ± 8.300F 359.334 ± 45.100G 355.102 ± 91.381G 571.1163 ± 7.045H 531.078 ± 14.573I S S
PHO 2% 1.52 297.308 ± 9.962 S S S L Lf Lf
PHO 50% 1.52 275.468 ± 30.643J 273.113 ± 87.710J S S L S Lf
g g g g
STE 2% L L Lf Lf
g g g g g g g
STE 50% Lf
CS 2% 1.52 334.256 ± 12.795K 334.378 ± 29.027K S S L Lf Lf
CS 50% 1.52 319.997 ± 6.269L 246.848 ± 29.409M 581.273 ± 14.414N S L Lf Lf
a
L = liquid at time of analysis; S = solid caked at time of analysis.
b
Particle size is an average of triplicate analysis with standard deviation and is the D(0.9) value.
c
Samples are as indicated: ASC = sodium ascorbate; DIO = silicon dioxide; SIL = calcium silicate; PHO = calcium phosphate; STE = calcium stearate; CS = corn starch.
d
Sample ratios are indicated as follows: 2% = 98% ASC:2% anticaking agent; 50% = 50% ASC:50% anticaking agent.
e
RI = refractive index; utilized for particle size measurements.
f
Liquid solution present after 3 d.
g
Samples containing calcium stearate were not analyzed through the particle size analyzer due to its hydrophobicity, but samples were observed for visual effects.
ABCDEFGHIJKLMN
Capital letters indicate significant differences (P < 0.05) within a set of powder blends and not between different powder blends.

C1068 Journal of Food Science r Vol. 76, Nr. 7, 2011

Effect of anticaking agents on vitamin C. . .

It is also well known that fine powders show poor flowability
due to enhanced van der Waals forces and increased intramolecular
cohesion (Chen and others 2010). The addition of a flow agent,
especially hydrophobic, may decrease the intramolecular van der
Waals forces by increasing intermolecular interactions between
the anticaking agent and the host particle. If an anticaking agent
is bound to the host particle by van der Waals interactions, more
Effect of storage RH and anticaking agents on ASC
chemical stability
Storage RH had a significant effect (P < 0.05) on ASC stability
in all formulations. The final vitamin C concentrations over a
range of RHs (23%, 43%, 64%, 75%, 85%, and 98%) for ASC
with and without anticaking agents at both 2% and 50% w/w
ratios after 32 d at 22 ± 3 ◦ C are shown in Figure 4. As expected,

energy is required to pull apart the guest and host particles as in-
teraction between two host particles is decreased. Yang and others
(2005) found this to be true for the addition of a hydrophobic
silica powder to corn starch that increased flowability of the corn
starch. The hydrophobic nature of the silica, rich in alkyl groups,
led to less interactions and binding to the hydroxyl groups on the
surface of the corn starch. This led to less agglomeration and ad-
hesion forces. Increased surface coating also led to greater physical
stability (Yang and others 2005). As predicted by Yang and others
(2005), the hydrophobic calcium stearate, although not measured
in Table 2, was most effective at enhancing physical stability at ele-
vated RHs due to water repulsion. Thus, the observed differences
of physical stability in the ASC–anticaking agent blends is likely
a function of (1) the mechanism by which the anticaking agent
prevents caking, (2) how the anticaking agent interacts with water
(or its hydrophobicity), (3) the surface adhesion and coverage of
the host particle, and (4) the intermolecular interactions between
the anticaking agent and host particle.
C: Food Chemistry
the ASC alone was stable at and below 75% RH, below its RH0 ,
and degraded when the RH exceeded RH0 . Interestingly, some
ASC degradation occurred at 85% RH, near but below the RH0,
in samples that were found to sorb some moisture over time.
It is hypothesized that an impurity in the ASC (≥ 99.0% pure)
and/or moisture-induced degradation products contributed to the
enhanced moisture sorption at 85% RH, below RH0 , which could
have further contributed to enhanced degradation.
The chemical stability of the ASC in blends with anticaking
agents significantly (P < 0.05) varied from ASC alone at higher
RHs (75%, 85%, and 98%), but no significant differences (P >
0.05) were found at lower RHs (23%, 43%, and 64%) (Figure 4).
Above 64% RH, rapid moisture sorption occurred for blends of
ASC and anticaking agents (Figure 2A and B). Vitamin C degrades
through hydrolysis of the lactone ring structure, and the rate of
degradation increases with increasing temperature, moisture, and
pH (May 1998). Due to the synergistic moisture sorption effect
of the ASC–anticaking agent blends (Figure 2C and D) and the

A 110 Figure 4– Percent vitamin C remaining for

sodium ascorbate in single and binary mixtures
100 at 2% (A) and 50% (B) ratios with anticaking
90 agents held for 32 d at 22 ± 3 ◦ C at various
relative humidities. The type of anticaking
Vitamin C Remaining (%)

80 agent present in the mixture is shown by:

70 Calcium silicate; calcium stearate;
silicon dioxide; calcium phosphate;
60 cornstarch; sodium ascorbate (control).
50
40
30
20
10
0
20 30 40 50 60 70 80 90 100
Relative Humidity (%)

B 110
100
90
Vitamin C Remaining (%)

80
70
60
50
40
30
20
10
0
20 30 40 50 60 70 80 90 100
Relative Humidity (%)

Vol. 76, Nr. 7, 2011 r Journal of Food Science C1069

 Effect of anticaking agents on vitamin C. . .
moisture brought into the system by the individual anticaking
agents (Figure 1A), this increase in moisture above the 64% RH
could have enhanced the opening of the lactone ring structure of
the ASC (Fennema 1996), leading to chemical degradation of the
blends at RHs above 64% RH. With enough moisture present,
this degradation could have proceeded at RHs below the RH0 of
ASC.
C: Food Chemistry
The type and ratio of anticaking agent blended with ASC sig-
nificantly (P < 0.05) affected the ASC chemical stability. An im-
portant finding is that no anticaking agent improved the stability
of ASC at 75% or 85% RH, but some did improve ASC sta-
bility at 98% RH (Figure 4). A sample graph of the effect of
the anticaking agents over time at a specific RH (85% RH) on
the chemical stability of sodium ascorbate is shown in Figure 5.
The anticaking agent ratio of 50% w/w had a significantly (P <
0.05) more negative effect on the chemical stability of the ASC
than did the 2% ratio for all five anticaking agents at RHs at or
greater than 75%. Below this RH, the ASC was stable with the
addition of anticaking agents at both ratios. At 75%, 85%, and 98%
RH, all 5 anticaking agents at 50% ratio dramatically increased the
ASC degradation after a 32-d time period. At 75% RH for the
2% anticaking agent ratios, no significant differences were found
between the control ASC (with final concentration of 101.2%
± 5.8%) and ASC-STE blends (with 96.3% ± 5.4% remaining).
At 85% RH, CS at 2% w/w ratios was not statistically different
than ASC alone, having final concentrations of 82.6% ± 1.0% and
82.0% ± 4.9%, respectively. At 98% RH, the ASC in blends with
both CS and PHO at 50% ratios as well as CS, PHO, DIO, and
SIL at 2% ratios was more chemically stable than the ASC alone
(Figure 4), although no samples were physically stable at this RH.
It is known that some compounds are quite stable to degrada-
tion in the presence of high RHs when present as a pure powder
but degrade rapidly when physically mixed with other substances
and exposed to moisture. The classic example is acetylsalicylic
acid, one of the most studied organic compounds. As a crystalline
powder, it is stable at high RH for several months; however, on
mixing with (seemingly inert) additives, the degradation rate is
accelerated (Mitrevej and Hollenbeck 1983). Despite numerous
studies with this compound, the mechanism of the enhanced sus-
ceptibility to degradation on exposure to moisture in the presence
of additives has not been elucidated. It appears that the sodium
ascorbate followed this trend—it was more stable alone at 75% and
85% RH than it was at these RHs when blended with anticaking
110
105
100
Vitamin C Remaining (%)
95
90
85
80
75
70
65
60
0 5 10 15 20 25
Time (Days)
C1070 Journal of Food Science r Vol. 76, Nr. 7, 2011
agents. Attempts were made to better understand the mechanism
of enhanced vitamin degradation in the presence of anticaking
agents at these RHs, investigating the consistency of trends be-
tween chemical and physical stability, moisture sorption, amount
of ASC dissolved, and microenvironmental pH.
The physical and chemical stabilities of ASC blends were af-
fected differently by the type and ratio of the anticaking agent.
The lower anticaking agent ratio (2%) led to higher chemical
stability of the ASC than the higher ratio (although neither im-
proved the stability of the ASC at 75% or 85% RH), while the
higher ratio (50%) led to greater physical stability. Compared to
the chemical stability of ASC–anticaking agent blends, physical
stability degraded at a faster rate at 75% and 85% RH than did
chemical stability (Figure 4 and 5 and Table 2). This may be seen
through the solid cake and/or liquid solution formation of the
samples before dramatic chemical degradation occurred. At 85%
RH after 2 wk, 98ASC:2STE formed a liquid solution (Table
2) while the chemical stability remained at 93.3% ± 0.63% after
16 d (Figure 5). At 75% RH after 4 wk, 98ASC:2SIL formed a
liquid solution (Table 2) but retained a vitamin C concentration
of 81.9% ± 3.1% after 32 d (Figure 4A). At 98% RH, signifi-
cant degradation was seen in both chemical and physical stability
for all samples except for 98ASC:2CS, in which liquefaction oc-
curred within 3 d (Table 2) while the vitamin C concentration
remained at 81.2% ± 3.8% after 32 d (Figure 4A). Overall SIL
and DIO were most effective at preventing physical degradation
at lower RHs (75% and 85%) but were ineffective at preventing
chemical degradation at the experimental RHs. CS and STE were
most effective at preserving chemical stability at 75% and 85% RH
compared to all other blends (although were less stable or the same
as ASC alone) and maintained moderate physical stability.
It could be assumed that the moisture sorbed by each mixture at
given RHs would be the most influential cause of chemical degra-
dation, but the percent moisture sorbed did not directly correlate
to the extent of chemical degradation (Figure 6). ASC:CS and
ASC:PHO (98:2% w/w) sorbed the largest amount of moisture,
93.7% ± 1.4% and 94.4% ± 4.6%, respectively, but still main-
tained the two highest levels of chemical stability at 98% RH
at 25 ◦ C after 32 d, with 81.2% ± 3.8% and 62.0% ± 8.3%
vitamin C remaining, respectively. On the other hand, ASC:STE
(98:2% w/w) and ASC alone sorbed the least amount of moisture,
83.0% ± 1.5% and 77.1% ± 7.0%, respectively, but had the high-
est amount of chemical degradation, 31.6% ± 0.2% and 30.0% ±
Figure 5– The chemical stability over time for
sodium ascorbate with and without 2% w/w
anticaking agents held at 85% RH and 22 ± 3 ◦ C
for up to 32 d. Mixtures are indicated by:
Sodium ascorbate; calcium stearate;
silicon dioxide; calcium silicate;
calcium phosphate; cornstarch.
30 35
Effect of anticaking agents on vitamin C. . .

0.7% vitamin C remaining, respectively. Hence, moisture uptake
is not the sole contributing factor for determining the effects of
anticaking agents on the chemical stability of vitamin C although
it plays a key role. Because the anticaking agents were known to
have different surface pH characteristics (Table 3), a separate study
was undertaken to explore the effects of pH on the stability of
sodium ascorbate in saturated conditions.
Another interesting observation in this study was that the 50:50
ASC:PHO blends stored at 98% RH consistently contained higher
vitamin C concentrations over time compared to samples stored
at 85% RH (Figure 4). One possible explanation for this may be
a salt switch between sodium ascorbate and tricalcium phosphate.
If conversion was to calcium ascorbate, then its deliquescent point
of 94% RH and altered structure could indicate a possible rea-

Solid and dissolved ingredients degrade at different rates (Guer-
rieri and others 2010). In these storage studies, the samples were
not at equilibrium but were sorbing moisture over time (Figure 3);
thus, the ratio of solid to solution changed over time. The per-
cent of the ASC sample dissolved in solution versus storage RH
and percent ASC remaining was plotted in Figure 7A–F for ASC
with and without 2% anticaking agents. For all mixtures sorbing
greater than 8% moisture (equivalent to 0.9 mmol of water for
every 1 mmol of solid, which is similar to previous studies; Hiatt
and others 2010b), significant chemical degradation (P < 0.05)
was seen, except for the 98:2 ASC:CS blend, which sorbed large
amounts of moisture but had no significant chemical degradation
(P > 0.05). All single and binary mixtures sorbed relatively small
amounts of water at lower RHs (23%, 43%, and 64%), thus little
ASC dissolved, and the samples were chemically stable. As storage
RH increased above 64% RH, variations were seen in moisture
sorption between sample types. Mixtures containing 2% DIO,
SIL, or PHO sorbed significantly (P < 0.05) more moisture at
75% RH than the other samples, decreasing the chemical stability
of ASC. Samples of ASC alone and mixtures with CS and STE
did not begin to dissolve until 85% RH. For SIL and DIO 2%
ratios with ASC, the percent ASC degradation and the percent
ASC dissolved intersect around 50%. This indicates that for these
two samples, the percent degradation corresponds to the percent
dissolved (Figure 7B–C). For ASC alone and blended with STE,
the percent degradation and percent dissolved intersect below the
50% mark, indicating that degradation occurred at a faster rate
than dissolution. These results, as well as those from the saturated
solution samples, indicated that dissolution is an important factor
C: Food Chemistry
son for better stability at higher RHs (Hiatt and others 2010a).
Another possible conversion may be to ascorbate polyphosphate.
In a study conducted by Wang and others (1995), ascorbic acid
readily converted to ascorbate 2-polyphosphate through the reac-
tion with sodium trimetaphosphate at ambient temperatures and
basic pH conditions. The altered stability was not observed in the
98:2 ASC:PHO blends, possibly due to the limited amount of cal-
cium phosphate present. However, due to the undesirable physical
changes that occurred in the PHO blends at elevated RH levels
(Table 2), this aspect was not further investigated.
Effect of pH on sodium ascorbate stability in saturated
solutions
It is well known that vitamin C is affected by pH, and the lac-
tone ring structure of the vitamin degrades more rapidly in more
basic conditions (Niemela 1987; Fennema 1996; May 1998). The
anticaking agents had different surface pH traits (Table 3), and
the type of anticaking agent significantly affected vitamin C sta-
bility (Figure 4 and 5). Thus, a separate study was conducted to
determine if different pH conditions in saturated solutions could
explain the variable effects of the anticaking agents on the vita-
min C stability. Saturated solutions ranging from pH 5 to 9 were
Table 3 – Saturated solution pH for single and binary mixtures of
sodium ascorbate and anticaking agents.
Saturated pH of 50:50 pH of 98:2
Sample solution pH blend with ASC blend with ASC
Sodium ascorbate 7.83 ± 0.17 a a

in the chemical stability of ASC. The degradation rate proceeded Calcium phosphate 6.68 ± 0.07 6.78 ± 0.05 7.41 ± 0.09
faster in the solution state, which is consistent with previous re- Calcium silicate 9.42 ± 0.14 8.84 ± 0.26 8.30 ± 0.16
ports of dissolution and chemical stability (Ortiz and others 2009). Calcium stearate b b
8.01 ± 0.07
The chemical stability may be correlated to the ratio of saturated Corn starch 5.74 ± 0.30 7.07 ± 0.30 7.70 ± 0.01
Silicon dioxide 6.21 ± 0.01 6.30 ± 0.08 6.90 ± 0.45
solution to powder form (Guerrieri and others 2010; Hiatt and a
Sample utilized as the control for the blends.
others 2010b). b
Sample not measured due to hydrophobic nature and inability to form a saturated
solution.

110 Figure 6– Percent vitamin C content remaining

versus moisture sorbed after 32 d at 22 ± 3 ◦ C
100 and 23% to 98% RH for sodium ascorbate with
90 and without 2% w/w anticaking agents.
Calcium silicate; calcium stearate. Blends
Vitamin C Remaining (%)

80 shown by: silicon dioxide; calcium

70 phosphate; cornstarch; sodium
ascorbate (control).
60

50

40

30

20

10

0
0 10 20 30 40 50 60 70 80 90 100 110
Moisture Sorption (%)

Vol. 76, Nr. 7, 2011 r Journal of Food Science C1071

 Effect of anticaking agents on vitamin C. . .
prepared to determine the effects of the pH, encompassing the
pH range of the blends (Table 3), on the chemical stability of the
vitamin C over time (Figure 8). For comparison, the pH of a sat-
urated solution of ASC alone was 7.8 (Table 3). The final vitamin
C concentrations after 32 d at 25 ◦ C for the various pH saturated
solutions decreased with increasing pH (Table 4). The ASC sta-
bility at pH 8 and 9 was not significantly different (P > 0.05),
C: Food Chemistry
with 67.6% ± 2.7% and 65.7% ± 1.7% ASC remaining after 32 d,
respectively. However, ASC was significantly (P < 0.05) less stable
at these pHs than at the lower pHs studied, as expected at these
basic conditions (Niemela 1987; Fennema 1996; May 1998). At
pHs below 8, ASC stability significantly (P < 0.05) increased as
pH decreased.
It would, therefore, be expected that if the anticaking agents al-
tered the pH of the microenvironment around the ASC, then ASC
stability would be affected. The saturated solution pH of the vari-
ous forms of anticaking agents with ASC would also be expected
Figure 7– Comparison of percent sodium ascorbate remaining and theoretical percent dissolved after 32 d at 22 ± 3 ◦ C for various relative humidities
for sodium ascorbate (A) alone and with anticaking agents at 2% w/w: silicon dioxide (B), calcium silicate (C), calcium phosphate (D), calcium stearate
(E), and corn starch (F). Percent remaining and dissolution are indicated as follows:
C1072 Journal of Food Science r Vol. 76, Nr. 7, 2011
to have an effect on the final vitamin C concentration. According
to Hailu and Bogner (2009), solid-state surface acidity is a measure
of the “microenvironmental pH” between two powders within a
system, and the saturated solution pH is an approximation of the
Table 4 – Final vitamin C concentration for various pH buffered
saturated solutions of sodium ascorbate after 32 d at 22 ± 3 ◦ C.
pHab Final vitamin C concentration (%)
5 81.0 ± 4.1W
6 77.7 ± 2.7X
7 74.6 ± 0.2Y
8 67.6 ± 2.7Z
9 65.7 ± 1.7Z
Control ASC 7.8 67.2 ± 0.001Z
a
pH was determine through an IQ Scientific Instrument IQ 150 pH/mV/Thermometer
pH meter with ISFET sensory probe calibrated at pH levels of 4, 7, and 10.
b
Samplerepresents a saturated solution of sodium ascorbate held at a specified pH value.
Letters indicate a statistical difference with an α = 0.05.
W,X,Y,Z
% remaining; dissolved.
Effect of anticaking agents on vitamin C. . .
proton activity within the system. This describes the effect of the
pH on the surface of each powder, such as ASC and an anticaking
agent, and the effect of the interaction between the two (Guer-
rieri and others 2010). The saturated solution pH was measured
for individual and binary mixtures of ASC and anticaking agents
(Table 3). For the single ingredients, there was a wide range of
pH values. In the ASC blends containing 2% anticaking agent,
the pH of the mixture was still affected by the initial pH of the
anticaking agent. When comparing the saturated solution pHs of
the ASC–2% anticaking agent blends (Table 3), the 2% DIO and
2% SIL blends would be expected to be the most and least stable
because they had the lowest and highest saturated solution pHs of
6.90 ± 0.45 and 8.30 ± 0.16, respectively. However, the final vi-
tamin C concentration in these powder blends stored at 85% RH
after 32 d was not representative of this, with final concentrations
of 64.4% ± 3.6% and 70.0% ± 3.6%, respectively (Figure 4A and
5). These samples were significantly less stable than ASC alone,
with a pH of approximately 7.8 and a final vitamin C concentra-
tion of 82.0% ± 5.0%. Blends containing 2% CS had the closest
saturated solution pH to that of ASC alone, with a pH of 7.70 ±
0.01, and the chemical stability of these samples was comparable to
ASC alone, with 82.6% ± 1.0% remaining after 32 d at 85% RH.
These results indicate that ASC in blends may be more stable if the
saturated solution pH is closer to that of the saturated solution of
ASC alone, although saturated solution pH and chemical stability
were not directly correlated.
In a study conducted by Guerrieri and others (2010), it was de-
termined that the saturated solution pH affects both the chemical
stability and the dissolution of a deliquescent salt. When com-
paring the saturated solution pH for each 2% anticaking agent
mixture with ASC (Table 3) to the dissolution rate (Figure 7A–F),
the increased dissolution rate did not directly correlate to the satu-
rated solution pH. The 2% DIO, PHO, and SIL mixtures had the
highest amount of ASC dissolution and degradation, but DIO had
the lowest saturated solution pH. However, the trends observed
for SIL and PHO blends are fairly consistent with the conclusions
from the literature (Guerrieri and others 2010). As previously ob-
served, moisture sorption, which is an indication for dissolution,
was a contributing factor for determining chemical and physi-
cal stability of ASC. However, the pH of the saturated solution
Figure 8– Percent vitamin C remaining for
sodium ascorbate in pH buffered saturated
solutions over time at 22 ± 3 ◦ C. pH 5;
pH 6; pH 7; pH 8. Solutions
shown by: pH 9.
C: Food Chemistry
did not directly correlate to the chemical stability or dissolution
rate. Therefore, other outside factors may also contribute to the
chemical and physical stability of the powdered vitamin C.
Conclusion
Anticaking agent type and ratio significantly (P < 0.05) affected
the physical and chemical stability of ASC over time and over a
range of RHs. Interestingly, the addition of anticaking agents to
ASC increased the moisture sorption above, at, and below RH0
but did not significantly alter the deliquescence point of ASC.
The higher concentration (50% w/w) of anticaking agents led to
increased moisture sorption but also enhanced the physical stabil-
ity of the powder blends. Unfortunately, the increased moisture
sorption and/or other conditions encountered in the blends led
to decreased ASC chemical stability at and below the RH0 . Al-
though DIO and SIL at 50% w/w ratios were the most effective
at preserving physical stability, they were the least effective blends
at preserving chemical stability. The ASC blends containing 50%
w/w of anticaking agents had greater chemical degradation than
the 2% w/w blends. STE and CS at 2% w/w ratios retained bet-
ter ASC chemical stability than the other anticaking agent:ASC
blends (although did not improve the ASC stability compared
to ASC alone). These blends also improved the physical stability
compared to ASC alone. Therefore, of the anticaking agents inves-
tigated, STE and CS at 2% ratios are the recommended anticaking
agents to use in combination with ASC powder if storage envi-
ronmental conditions could encounter 75% or 85% RH. Storage
of samples at 98% RH should be avoided.
This is the first study accounting for both physical and chemi-
cal stability of a deliquescent ingredient blended with anticaking
agents. This is important to note because much is known about
the effects of anticaking agents on the physical stability of pow-
der systems, but not much information is known about the effect
of anticaking agents on chemical stability. Because the anticaking
agents significantly affected the chemical stability of the vitamin
C, it could be possible that anticaking agents would greatly affect
other chemically labile deliquescent ingredients, and therefore, an-
ticaking agent usage and storage conditions should be monitored
in blended powder systems.
Vol. 76, Nr. 7, 2011 r Journal of Food Science C1073
 Effect of anticaking agents on vitamin C. . .
Acknowledgments
The authors acknowledge support by USDA-NRICGP Grant
nr 07-35503-18405 and the Purdue Univ. Faculty Scholars pro-
gram. Dr. Ganesan Narsimhan is thanked for providing use of the
Malvern Mastersizer 2000 particle size analyzer.
References
C: Food Chemistry
Adhikari B, Howes T, Bhandari B & Truong V. 2001. Stickiness in Foods: A Review of
Mechanisms and Test Methods. International Journal of Food Properties 4(1):1–33.
Aguilera J, del Valle J & Karel M. 1995. Caking Phenomena in Amorphous Food Powders.
Trends in Food Science and Technology 6(7):149–155.
Ash M & Ash I. 2008. Handbook of Food Additives (3rd Edition). Endicott: Synapse Information
Resources, Inc.
Barbosa-Canovas G, Ortega-Rivas C, Juliano P & Yan H. 2005. Food Powders: Physical Prop-
erties, Processing, and Functionality. New York: Kluwer Academics/Plenum Publishers.
Chen Y & Chou J. 1993. Selection of anti-caking agents through crystallization. Powder Tehc-
nology 77(1):1–6.
Chen Y, Jallo L, Quintanilla MAS & Dave R. 2010. Characterization of particle and bulk level
cohesion reduction of surface modified fine aluminum powders. Colloids and Surfaces A:
Physicochemical and Engineering Aspects 361(1–3):66–80.
FDA. 2011. Anticaking Agents. Code of Federal Regulations Title 21, Volume 3. Part 172
Subpart E. 21CFR172.480
Fennema O. 1996. Fennema’s Food Chemistry Fourth Edition. Boca Raton: CRC Press.
Foster MC & Ewing GE. 2000. Adsorption of water on the NaCl(001) surface. II. An infrared
study at ambient temperatures. Journal of Chemical Physics 112(15):6817–6826.
Guerrieri P, Jarring K & Taylor LS. 2010. Impact of Counterion on the Chemical Stability of
Crystalline Salts of Procaine. Journal of Pharmaceutical Sciences 99(9):3719–3730.
Hailu S & Bogner R. 2009. Solid-State Surface Acidity and pH-Stability Profiles of Amor-
phous Quinapril Hydrochloride and Silicate Formulations. Journal of Pharmaceutical Sciences
99(6):2786–2799.
Hansen L, Hoffman F & Strathdee G. 1998. Effects of Anticaking Agents on the Thermodynam-
ics and Kinetics of Water Sorption by Potash Fertilizers. Powder Technology 98(1):79–82.
Hersey J. 1975. Ordered Mixing: A New Concept in Powder Practice. Powder Technology
11:41–44.
Hiatt A, Ferruzzi M, Taylor L & Mauer L. 2008. Impact of Delliquescence on the Cheimcal
Stability of Vitamins B1, B6, and C in Powder Blends. Journal of Agricultural and Food
Chemistry 56(15):6471–6479.
Hiatt A, Ferruzzi M, Taylor L & Mauer L. 2010a. Deliquescenc Behavior and Chemical Stability
of Vitamin C Forms (Ascorbic Acid, Sodium Ascorbate, and Calcium Ascorbate) and Blends.
International Journal of Food Properties [serial online]. DOI:10.1080/10942911003650338.
Available from Taylor and Francis Group (tandf.co.uk). Posted Dec 1, 2010.
Hiatt AN, Taylor LS & Mauer LJ. 2010b. Influence of Simultaneous Variations in Temperature
and Relative Humidity on Chemical Stability of Two Vitamin C Forms and Implications for
Shelf Life Models. Journal of Agricultural and Food Chemistry 58(6):3532–3540.
Hui YH. 2006. Handbook of Food Science, Technology, and Engineering, Volume 4. Boca
Raton: CRC Press.
Irani R, Callis C & Liu T. 1959. How to select Flow Conditioning and Anticaking Agents.
Industrial and Engineering Chemistry 51(10):1285–1288.
Kampuse S, Kampuss K & Pizika L. 2002. Stability of anthocyanins and ascorbic acid in raspberry
and blackcurrant cultivars during frozen storage. In: Brennan, R. M., Gordon, S. L. &
C1074 Journal of Food Science r Vol. 76, Nr. 7, 2011
Williamson, B., editors. Proceedings of the Eighth International Rubus and Ribes Symposium,
Vols 1 and 2. Leuven 1: International Society Horticultural Science. p. 507–510.
Kitao S, Teramoto M, Yamaguchi T, Takamura H & Matoba T. 2006. Stabilizing effect of grape
seed extract on ascorbic acid. Food Science and Technology Research 12(1):15–21.
Kranl K, Schlesier K, Bitsch R, Hermann H, Rohe M & Böhm V. 2005. Comparing antiox-
idative food additives and secondary plant products – use of different assays. Food Chemistry
93(1):171–175.
Kwok K, Mauer LJ & Taylor LS. 2010. Kinetics of Moisture-Induced Hydrolysis in
Powder Blends Stored at and below the Deliquescence Relative Humidity: Investiga-
tion of Sucrose−Citric Acid Mixtures. Journal of Agricultural and Food Chemistry
58(22):11716–11724.
Mauer LJ & Taylor LS. 2010. Water-Solids Interactions: Deliquescence. Annual Review of Food
Science and Technology, Vol 1. Palo Alto: Annual Reviews. p. 41–63.
May JM. 1998. Ascorbate Function and Metabolism in the Human Erythrocyte. Frontiers in
Bioscience 3:D1-D10.
Mitrevej A & Hollenbeck R. 1983. Influence of Hydrophilic Excipients on the Interation of
Aspirin and Water. International Journal of Pharmaceutics 14:243–250.
Niemela K. 1987. Oxidative and nonoxidative Alkali-Catalyzed Degradation of L-Ascorbic-
Acid. Journal of Chromatography 399:235–243.
Ogur R, Saygi S, Gocgeldi E, Korkmaz A, Ucar M & Tekbas OF. 2008. Investigation of salts in
market for appropriateness with related laws, and contents. Turkiye Klinikleri Tip Bilimleri
Dergisi 28(2):137–142.
Ortiz J, Kestur US, Taylor LS & Mauer LJ. 2009. Interaction of Environmental Mois-
ture with Powdered Green Tea Formulations: Relationship between Catechin Stability
and Moisture-induced Phase Transformations. Journal of Agricultural and Food Chemistry
57(11):4691–4697.
Peleg M & Hollenbach A. 1984. Flow Conditioners and Anticaking Agents. Food Technology
38(3):93–102.
Peleg M & Mannheim C. 1973. Effect of Conditioners on the Flow Properties of Powdered
Sucrose. Powder Technology 7(1):45–50.
Polinati RM, Faller ALK & Fialho E. 2010. The effect of freezing at-18 degrees C and-70
degrees C with and without ascorbic acid on the stability of antioxidant in extracts of apple
and orange fruits. International Journal of Food Science and Technology 45(9):1814–1820.
Riaz M, Asif M & Ali R. 2009. Stability of Vitamins during Extrusion. Critical Reviews in
Food Science and Nutrition 49(4):361–368.
Salameh AK, Mauer LJ & Taylor LS. 2006. Deliquescence lowering in food ingredient mixtures.
Journal of Food Science 71(1):E10-E16.
Salameh AK & Taylor LS. 2005. Deliquescence in Binary Mixtures. Pharmaceutical Research
22(2):318–324.
Stevens R, Buret M, Garchery C, Carretero Y & Causse M. 2006. Technique for Rapid, Small-
Scale Analysis of Vitamin C Levels in Fruit and Application to Tomato Mutant Collection.
Journal of Agriculture and Food Chemistry 54(17):6159–6165.
Tang I & Munkelwitz H. 1993. Composition and Temperature-Dependence of the Deliques-
cence Properties of Hygroscopic Aerosols. Atmos Environment Part A 27:467–473.
Wahl M, Brockel U, Brendel L & Feise HJ. 2008. Understanding Powder Caking: Predicting
Caking Strength from Individual Particle Contacts. Powder Technology 188(2):147–152.
Wang XY, Qian WW & Seib PA. 1995. An Improved Synthesis of L-Ascorbate 2-Polyphosphate.
Journal of Carbohydrate Chemistry 14(1):53–77.
Yang J, Sliva A, Banerjee A, Dave RN & Pfeffer R. 2005. Dry particle coating for improving
the flowability of cohesive powders. Powder Technology 158(1–3):21–33.
Zografi G. 1988. States of Water Associated with Solids. Drug Development and Industrial
Pharmacy 14(14):1905–1926.