Effect of Concentration

and Pressure on the Boiling Point

Rise of Apple Juice and Related Sugar Solutions
G.H. CRAPISTE

ABSTRACT
An experimental procedure is proposed for the measurement of the
boiling point of clarified fruit juices, minimizing hydrolysis of sucrose. Boiling point rises of glucose, fructose, and sucrose solutions
and clarified apple juice were determined at different pressures and
concentrations, ranging from 72 to 700 mbar and 17 to 72 Brix,
respectively. Experimental results indicated that both concentration
and pressure significantly affect boiling point elevation. Applicability
of theoretical and empirical expressions to represent the experimental
behavior was analyzed. Sugar solutions behaved ideally up to approximately 35%. A method was proposed to predict boiling point
rise of apple juice from experimental data for the basic sugar components.

INTRODUCTION
At present, nearly 300,000 tons/year of apples produced in
Argentina are processed to clarified apple juice concentrate in
order to reduce shipment cost and increase shelf life. Multiple
effect evaporators are currently used in fruit juice processing
plants to eliminate water under vacuum at reduced temperatures without changing the solids composition. However, in
actual practice clarified apple juices are susceptible to deterioration during concentration (Lozano et al., 1984; Toribio and
Lozano, 1986). This process can be optimally designed and
efficiently operated if thermophysical and thermodynamic
properties of juices, in particular the boiling point or boiling
point rise, are known.
Information on boiling point rise (AT,) of fruit juices, especially apple juice, at the conditions usually found in commercial evaporators is not readily available. Previous literature
was addressed to other fruit juices (Varshney and Barhate,
1978; Moresi and Spinosi, 1980, 1984) and no attempt was
made to predict AT, of fruit juices from the knowledge of their
main nonelectrolyte components other than sucrose, the only
sugar solution of which an extensive study has been made
(Dunning et al., 1951; Honig, 19.53; Kadlec et al., 1981).
The purpose of the present work was: (1) to measure the
boiling point rise of clarified apple juice as a function of pressure and concentration of soluble solids, (2) to correlate the
results and compare them with those of pure sugars solutions,
and (3) to obtain predictions of AT, from the known chemical
composition of the juice.
Theoretical considerations
Clarified apple juice is essentially an aqueous solution of
various nonvolatiles, mainly fructose, glucose, sucrose, and
malic acid, in equilibrium with water vapor at the boiling point.
Any other volatile aromatic compounds, naturally present in
the fruit, are stripped out previously to the enzymatic clarification and can be considered negligible in the final product.
Then, only the influence of soluble solids in the boiling point
will be considered.
Two different methods can be used to describe the boiling
point elevation of sugar solutions and fruit juices as a function
of pressure (or boiling point of water) and concentration of
The authors are with PLAPIQUI (UNS-CONICET),
1842, 8000 Bahia Blanca, Argentina.

12 de Octubre

and J.E. LOZANO

soluble solids. In the first approach, empirical correlations are

presented to fit the experimental data on vapor-liquid equilibrium of solutions. The use of expressions suitable for describing the vapor pressureof pure water can be extendedto aqueous
solutions. Thus, a correlation derived from the Clausius-Clapeyron equation can be expressed in the form:
In P = A(W) - B(W)/T

(1)

or the Antoine equation, which can be written as:

In P = A(W) - B(W)/(T + C(W))

(2)
In these equations P is the pressure (mbar), T the temperature
of ebullition (K) and W represents the mass concentration of
soluble solids (% by weight or Brix). Obviously, more complex and accurate correlations can be proposed. However,
coefficients like A, B, and C in Eq. (1) and (2) result in
complex functions of concentration and only in particular cases
(Moresi and Spinosi, 1984) the boiling point can be explicitly
obtained from those expressions. In addition, a best representation can be obtained if the boiling point rise instead the temperature of ebullition is used in fitting the data. For the above
reasons an empirical equation of the form:
AT, = 01Waexp(yW) P

(3)

is proposed in this study, where AT, is the boiling point rise

(C) and the parameters (Y, p, y and 6 will be evaluated from
experimental information.
In the second approach, theoretical expressions are derived
to estimate the extent of the boiling point elevation in solutions. From thermodynamic considerations it can be shown that
the integral form of the boiling point rise equation is given by:
In a, = %

(l/T - I/-L)

where a,,, is the water activity, AH, the latent heat of evaporation of water (KcaUKg mole), R the gas constant (1.987
Kcal/kg mole C) and T,,, the boiling point of pure water (K).
From Eq. (4) the boiling point rise can be explicitly evaluated
as:
AT,=

-TV
1 + (AH,/RT,ln

T - T,=

a,..)

(5)

For the particular case of ideal solutions, using Raoults law,

Eq. (5) results:
-TV
AT, =
(6)
1 + (AH,/RT,ln x,J
and for diluted ideal solutions this equation can be simplified
to:
AT,=

%(I

- xH)

(7)

where & is the mole fraction of water. Equations (6) and (7)
are simplified forms of the boiling point rise equation, only
valid for ideal solutions. They require knowledge of the mole

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fraction of solute but they are independent of the kind of solute.

Their applicability will be checked on real sugar solutions.
Equation (5) can be used to predict the boiling point elevation if water activity of the solution as a function of temperature and concentrationis known. However, this experimental
information is not easily available and, from a practical standpoint, interest is focused in those equations from which AT,
can be calculated in a simple and noniterative way. This requirement leaves out of consideration in this study the above
theoretical procedure and those methods based in a thermodynamic treatment of multicomponent systems, like that proposed by Kadlec et al. (1981), where interaction coefficients
between components should be known. This kind of approach
will be considered in a future work. However, Eq. (5) will be
used in this work to develop a relatively simple method to
estimate the boiling point rise of fruit juices in terms of the
experimental data for the individual solutions. Although several expressions have been presented for predicting water activity of multicomponent aqueous solutions (Teng and Seow,
1981), the equation proposed by Ross (1975) is considered
here because of its reasonable accuracy and particulary simple
form. This equation can be expressed as:
h = II

(%A

(8)

where (~)i represents the water activity of a binary solutions

of i component at the same concentration and temperature as
in the multicomponent solution. Substitution of Eq. (8) into
Eq. (5) allows us to obtain:
ATJT,

= S/(1 - S)

The separation of vapor and liquid phases was achieved by using a

Cottreli pump. Temperatures were measured and recorded with a pi&
inum resistance transducer coupled to a high precision digital temperature meter (System teknik S 1220, SWEDEN) and a Varian Mod
9176 Recorder. The inaccuracy was estimated not to exceed t 0.015C.
A positive displacement type vacuum pump was used to evacuate the
boiling recirculation apparatus. Vacuum was controlled with a NORMAG digital controller in the range XI-1014 mbar (-c 0.1 mbar).
Experimental

procedure

The technique of ebullimetric determination of boiling point, based

on the use of Cottrells apparatus, has been used previously with fruit
juices (Varshney and Barhate, 1978; Moresi and Spinosi, 1980, 1984).
In the present study the experimental conditions were established to
meet the following basic requirements, not fully satisfied in the methods described in the above mentioned papers: (1) minimum inversion
of sucrose and (2) precise determination of soluble solids just at the
point of vapor-liquid equilibrium temperature measurement. The operating principle of the apparatus was described extensively by Rock
(1960). However, high viscosity solutions, like apple juice concentrate, required some special conditions. Rate of heating had to be
adjusted so that the flow of condensate was 2-3 drops per set, in
order to completely recirculate the 240 mL liquid sample in 2-4 min.
Stirring also had to be carefully controlled to damp out oscillations of
the level in the sample vessel where the liquid is collected just after
the vapor-liquid separation at the actual concentration. At least two
determination of soluble solids were made during each run by extracting 0.2 mL sample with a syringe. The method was inaccurate below
70 mbars due to the poor boiling characteristics of concentrated juices
and sugar solutions. No more than 15 min were necessary to reach
the equilibrium temperature even under poor boiling conditions.

(9)
RESULTS & DISCUSSIONS

with

THE EXPERIMENTAL METHOD was check with water and

sucrose solutions whose boiling points at various vacua and
so that AT, of complex solutions like apple juice can be predicted from the known chemical composition and the boiling
point elevations of binary aqueous solutions of the main components at the same pressure and concentration as in the complex solution. It can be proved that under conditions in which
ATJT,

< < 1, a reasonable consideration in most practical cases,

Eq. (9) can be approximated by:

AT,=

MATERIALS

CAT,i
L

Table 1 -Specifications

of the applk juice concentrate

Soluble solids, Brix

Reducing sugars, g/kg
Total sugars, g/kg
Total acidity, g/L
Total phenolics, ppm
Total aminoacids. mea/L

12.0
91.50
107.67
6.00
6.89
7.6

a Redilutsd to 12 Brix

(10)

& METHODS

Materials
X CONDENSER

Apple juice concentratewas obtained from commercial sources(Coop.

Julia y Echarren, Buenos Aires, Argentina). Samples with various
degrees of soluble solids were made by reconstituting the 72 Brix
concentrate with distilled water. Solutions of sucrose, fructose and
glucose were prepared with pure sugars and distilled water. All chemicals and reagents were analytical grade from Sigma Chem. Co. (St.
Louis, MO, USA).

COOLING
WATER
IN

Physical and chemical analysis

Soluble solids were measured as Brix (juice) or refractive index

nnZo(sugar solutions) with a bench refractometer at 20 + O.lC. Total
acidity, pH, total sugars and reducing sugars were determined according to AOAC (1980) methods. Table 1 summarize the characteristics of the apple juice used in this work.

WATER aAni

Apparatus

The experimental determination of the boiling point was carried out

with a circulation apparatus for the measurement bf vapor-liquid equilibrium (NORMAG A.G.), similar to that described by Rock and Sieg
(1955) and designed to eliminate problems due to large heat fluxes.
A diagrammatic sketch of the experimental setup is shown in Fig. 1.
866-JOURNAL

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MAGNETIC
STIRRER

Fig. 1 -Schematic
diagram
point determinations.

of the experimental

setup for boiling

concentrations are known (Honig, 1953; Chau, 1980), with

excellent results. The boiling point was determined at 73,123,
199, 311, 473 and 700 mbar, corresponding to the water boiling points in the range of 40-90 C. The boiling point rise was
calculated as the difference between the boiling points of the
solution and water at the same pressure.
Fruit juices have different amounts of sucrose, reducing sugars and organic acids (Mattick and Moyer, 1983). When they
are heated, acid catalysed hydrolysis of sucrose occurs at a
rate which is a function of temperature, concentration and pH.
If water is present in excess, as in juices, sucrose hydrolysis
follows a psuedo first order equation. Temperature dependence
can be described by the Arrhenius equation with an activation
energy value of approximately 26.5 KcaVmol as determined
by Schoebel et al. (1969) for a saturated solution catalyzed by
citric acid. Babsky et al. (1986) indicated that pH significantly
affected the rate of hydrolysis and reported the dependenceof
the first order rate constant on pH. Inversion can be neglected
in experiments with pure sucrose solutions at moderate temperatures, as shown by Dunning et al. (1951) and confirmed
in the present work. However, on the basis of the above considerations it can be estimated that in an apple juice (pH =
3.5) heated from 40 to 100C for approximately 1 hr, which
represents the time elapsed for determining the boiling point
at different pressures keeping constant the soluble solids, up
to 50% of the initially present sucrose hydrolyzed. Boiling
point is a function of the molality of the solution and hydrolysis
strongly modifies the number of moles. Several runs were carried out to determine the optimal experimental conditions based
on the analysis of the sucrose content of samples before and
after heat treatment. Apple juice samples needed to be buffered
to pH = 5; the influence of the buffer on the boiling point
was undetectable.
Results of boiling points rises of sucrose and reducing sugars
solutions and clarified apple juice are shown in Fig. 2, 3 and
4. It can be seen that there is a very strong dependenceof AT,
with concentration and a noticeable increase with pressure (or
boiling point of water). The experimental values for sucrose
solutions (Fig. 2) are in agreement with the results presented
in previous extensive studies by Dunning et al. (1951) and

Honit; < 53). Since differences between AT, values for glucose and iructose soiutions were negligible, both sets of data
are represented in Fig. 3 as the boiling point elevation of reducing sugars. This can be explained on the basis of Eq. (5)
since, from the point of view of lowering water activity, fructose and glucose have a similar behavior (Riiegg and Blanc,
1981). Comparison of boiling point rises of apple juice and
sugar solutions at 700 mbar (Fig. 4) shows that AT, of apple
juice increased with concentration closer to the corresponding
reducing sugar values. On the other hand, a significant error,
up to 60% for a 72 Brix juiCe, could be introduced in the
estimation of AT, of apple juice by using the experimental
data of sucrose solution, a usual practice in process design.
This behavior can be explained by considering that the reducing sugars amounted to about 85% of the total sugars in apple
juice (Table 1).
The effect of pressure on the boiling point rise can be appreciated better by plotting AT, vs the boiling point of water
for different products at similar concentrations of soluble solids
(Fig. 5). Although the dependencewith T, is supported by the
previous thermodynamic considerations, the experimental results were in disagreement with published data for orange juice
(Moresi and Spinosi, 1980) and pineapple, mango, and lemon
juice (Varshney and Barhate, 1978). Reported independence
of AT, with T,,, and the anomalous results in Fig. 5 may be
attributed to partial hydrolysis of the sucrose, inaccurate reading of pressure and sample concentration, and, in general,
inaccurate experimental procedures.
Experimental data were fitted to the proposed empirical correlation given by Eq. (3) using a linear multiple regression
technique (Daniel and Wood, 1980). The resulting parameters

F
l

7;t
0

pressure

( m bar 1

7ccl
473
311

199

0
n

pressure (mbar)

700 mbar
473 mbar

PI
1%

mbar

73 mbar

50
CONCENTRATION,

50
CONCENTRATION, /a w/w

W/W

Fig. 2-Experimental
boiling point rise of sucrose solutions as
a function of concentration
and pressure. Proposed equation,
E9. /3), including Honig (1953) data (--);
theoretical predictions for ideal solutions, E9. (6), at 73 mbar (- - -1.

Fig. d-Effect
of concentration
on experimental
boiling point
rise of reducing sugars at different pressures. Proposed equation,
E9. (3) (--I;
theoretical predictions, E9. (6) at 73 mbar (- - -J.
Volume

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EFFECT ON CONCIPRESSURE ON BP RISE. . .

7

pressure ( m ba r 1

0 700
A 473
+ 311
0 199
0 123
0 73

pressure (mbar)

CONCENTRATDN,Brix
Fig. 6-Effect
of concentration
on the boiling point rise of apple
juice and model solution (reducing sugar/sucrose
= 5.66) at 123
and 700 mbar. Predictive values of E9. (9) and E9. (10) I-J;
theoretical predictions for ideal solutions, E9. (6) (-J.

Table .?- Values of parameters for evaluating boiling point rise of apple
juice and related sugar solutions with the proposed correlation4

50
CONCENTRATION Brix

ax102
Sucrose
Reducing sugars
Apple juice

Fig. I-Effect
of concentration
on the boiling point rise of clarified apple juice at different pressures. Proposed equation, (3),
for: apple juice at 73 and 700 mbar (-J; sucrose at 700 mbar (.-.-J; and reducing sugars at 700 mbar I-J.

..G

.-;y
rM&-o-

4
40

-:S

- -- --o
---O
A

.L?
A

I
60

80

P
0.09417

yx102

rzb

oc

5.329

0.1356
0.1186
0.1054

0.999
0.997
0.998

0.083
0.078
0.062

2.2271

0.5878

3.593

1.3602

0.7489

3.390

BAT, = (I wp explyW)Pa
brz = multipk correlation coefficient (squared\
Cg. = standard errcr

A
A

3.0612

100

BOILING POINT OF WATER, C

Fig. 5-Effect
of pressure on the boiling point rise. n Sucrose
solution, 60.1%; 0 Sucrose solution, 60% (Honig, 1953); l Reducing sugars solution, 59.3%; A Apple juice, 61.8% Brix; o
Orange juice, 57.5% &ix (Moresi and Spinosi, 1980); A Lemon
juice, 45 Brix (Varshney and Barhate, 1978).

and related coefficients of correlation are listed in Table 2. The

agreement between the AT, curves evaluated with eq. (3) and
the experimental data is shown in Fig. 2, 3 and 4. The proposed equation provides a simple means to represent AT, in

sugar solutions and fruit juices as a function of concentration

and pressure.
Theoretical AT, of ideal solutions predicted through Eq. (6)
and (7) are also compared wit the experimental data of sugar
solutions in Fig. 2 and 3. At relatively small concentrations of
sugars both equations gave practicalli the same results. As an
example, at & = 0.95 which corresponds to a 50% sucrose
solution and a 34.5% reducing sugar solution, differences between predictions are less than 0.5%. As expected, at higher
concentrations AT, was better predicted by Eq. (6). However,
coarse error of estimation should be expected for concentrated
solutions if ideal behavior is considered. It can be inferred that
solutions of single sugars behave as ideal up to approximately
35% and the simplified equation for dilute solutions safely
predicts AT, in this range.
Since the sugars are the most important constituents of fruit
juices the boiling point rise should be determined largely by
the type and concentration of sugars, which is suggested by
the results represented in Fig. 4. A further study was made to
evaluate the effect of the composition of apple juice on boiling
point rise. It consisted in the determination of AT, of a model
system made with water, sucrose and reducing sugars in the
same proportions present in the apple juice: reducing sugars/
sucrose ratio (R:S) equal to 5.66. Results (Fig. 6) indicated
that from a practical standpoint, R:S could be used for estimating AT, of clarified apple juice by means of an expression
valid for multicomponent systems as that proposed in Eq. (9).
The simplified model provided by Eq. (10) gave practically
the same predictions as Eq. (9). The AT, values predicted from
Eq. (6) are also shown in Fig. 6. The theoretical procedure
developed in this work closely predicted the variation of AT,
with concentration for the model system while some discrep-Continued

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