Correlations

of Enthalpies of Food Systems

H. D. CHANG and L. C. TAO

ABSTRACT
Correlations of enthalpies of food systems containing water fraction from 0.74-0.94 are presented for a temperature range 230-310K (-50 to 95F). with these correlations, energy requirement in freezing and thawing foods within the limits of data base used for this work may be computed by providing the identity of food group (meat, juice or vegetable/fruits), water content, initial, and final temperatures.

capacity above the freezing temperature and a curved portion below the freezing temperature.
Correlations below the freezing temperature are of inter-

INTRODUCTION
IN FREEZING AND THAWING FOODS, enthalpy properties are necessary data for computations involved in

process operation and equipment design. Since each species of food has its own physical structure and composition, the sets of data for natural and synthetic foods are numerous. To facilitate any systematic analysis or study of operation and design, it is desirable to make data reduction of available information so that a few sets of equations be available for process computation of a majority of food systems if not all. This article presents the findings of such correlations to cover enthalpy in a temperature range of approximately 230-310 K (-50 to 95 F) for meats, vegetables, fruits and juices with water fraction from 0.73-

0.94.

CORRELATIONSOFENTHALPYCHANGE ANDTEMPERATURE
A TYPICAL ENTHALPY FUNCTION versus temperature usually indicates a linear part representing a constant heat
Authors Chang and Tao are affiliated Engineering, Univ. of Nebraska, Lincoln, Table 1 -Physical propertiesa with the Dept. NE 68588. coefficients of Chemical

est as they involve the change of ice fraction. Reidel(195 1) correlated the enthalpies of vegetables and juices by assuming a correlation of ice fraction as a function of temperature. Woodrich (1966) proposed the use of an integral type of equation to fit data. In this study, a relatively siniple enthalpy-temperature equation is developed to cover most, if not all, food systems. Ice fraction can be calculated from the enthalpy equation as a consequence. This approach simplifies the use of these correlations since there will be only two independent parameters for input: water fraction and identity of food groups. Furthermore, it facilitates simulation (Joshi and Tao, 1974) type computation. Enthalpy is a relative quantity and the datum state is 227.6 (-50 K F) as used by Joshi and Tao (1974). For temperature below freezing, the following empirical equation of two dimensionless groups was used to correlate the enthalpy data. H, = a T, + (1 -a)Trb (1) where H, = H/Hf and T, = (T-227.6)/(Tf-227.6). (2) This equation assures H = Hf at the freezing temperature Tf. It has a steep slop dH,/dT, of a + (1 -a)b at the freezing temperature and changes smoothly to a small slope a at T, = 0. Data of 23 food systems tabulated by Dickerson (1968) were extrapolated to -50F from -4O for correlation F with Eq (1). The computed coefficients a, b are tabulated on Table 1. Figures 1 and 2 illustrate the correlations graphically for beef and orange juice. Ice fraction computation is discussed in the latter portion of this article. Analogous figures for other foods are available (Chang, 1977).
-Continued on nextpage

and correlation

Meat/Fish Group Food Vb Tf -4 C Beef 0.745 272.37 312.85 4046.1 0.31 22.0 Chicken 0.760 272.21 312.95 4094.3 0.30 21.4 Venison 0.730 272.26 302.85 4046.1 0.32 19.1 Veal 0.765 272.26 317.27 4093.4 0.31 22.97 Cod 0.803 272.37 332.62 4238.8 0.30 23.1 Haddock 0.836 272.43 345.88 4287.0 0.28 23.3 Group Apple sauce 0.828 271.48 347.74 4287.0 0.34 18.84 Pear 0.838 271.54 349.37 4287.0 0.33 19.16 Peach 0.851 271.59 354.25 4335.1 0.31 19.64 Onion 271 .Jl 0.855 356.81 4383.3 0.31 19.6 Grape 0.847 271.08 350.99 4383.3 0.32 i a.35 Cherry 0.867 271 .Jl 360.06 4431.5 0.31 19.26 Apple 0.872 272.71 361.46 4431.5 0.31 19.86

Juice Group Raspberry 0.885 271.93 369.37 4479.6 0.29 21.06 Orange 0.890 271.98 369.60 4479.6 0.29 21.3 Barberry 0.895 272.04 372.16 4479.6 0.28 21.6 Strawberry 0.917 272.26 381.70 4576.0 0.26 23.8

a
b

Vegetable/Fruit Food
b Tf

Tall pea 0.758 271.32 327.97 4094.3 0.36 19.2

1968 Fraction;

Strawberry 0.893 272.26 374.72 4527.8 0.27 24.2

Tf

Asparagus 0.926 272.48 383.32 4576.0 0.23 25.9

Tomato
PUlP

Carrots
0.875 272.04 365.18 4479.6 0.30 21.52

Spinach 0.902 272.59 374.25 4479.6 0.24 26.6

-4 C
a

0.929 272.43 387.74 4624.1 0.25 25.1

a Dickerson, by = Water

In OK;

Hf

in kJ/kg;

C In J/kg.K

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A further study of these coefficients indicates that they are related to water content and the food type. The latter characterizes the structure and composition of a food system. Figures 3 and 4 show the plots between the coefficients and water content for meat and nonmeat groups. The meat group includes fish. Equations to correlate these coefficients are as follows:

contents of foods. With the least square method, coefficients of a linear equation were calculated to include juices, vegetables, fruits, and meat. Eq (7) shows the correlation of data on Figure 5. Since the objective is to correlate food systems, no attempt was made to make C converging to that of water for y = 1.O. C = 1597.3 + 2583.3 y (7)

I.

Meatgroup a = 0.316 - 0.247(y-0.73) - 0.688(y-0.73)*

b = 22.95 + 54.68 (a-0.28) - 5589.03 (a-0.28)2

CORRELATIONS H, and T, OF (3) (4)

IN ORDER TO USE the equations developed above to compute enthalpy, it is necessary to find Hr and Tf of various foods systems. These variables are plotted versus water content on Figures 6 and 7 to compare with Eq (8) to (11). Hf = 9792.46 + 405,096 y (8)

Vegetables, fruits, juicesgroup

a = 0.362 + 0.0498 (y-0.73) - 3.465 (y-0.73)* (5) b = 27.2 -129.04 (a-0.23) - 481.46 (a-0.23)* (6) For enthalpy values above freezing, dH/dT = C which can be assumed to be independent of temperature. Dickerson (1968) correlated the data of juices as a function of

Meatgroup
Tf = 271.18 + 1.47~

(9)

. Y

.8.*

A data -eq 1 and Table

.a-

.2*.

data eq 12

0 0 .2

.4

Tr .6

.8

, I.0

O0.i

Tr b6

.i3

Fig. 1-Correcred

enrhalpy and ice fraction of beef.

eq.1

and

Table

.2

.4
OF FOOD

T .6 r

.8
Fig. Z-Corrected

1.0
enthalpy and ice fraction of orange juice.

.4

T -6
r

-8

l.(

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CORRELATION OF ENTHALPIES OF FOOD SYSTEMS.

Vegetable and fruit group 3c A meat l non-meat 27

Tf = 287.56 - 49.19 y + 37.07 y*

Juice group

(IO)

Tf = 120.47 + 327.35 y - 176.49 y*

(11)

COMPUTATION ENTHALPY OF
WITH THESE CORRELATIONS, one may thus compute the enthalpies of food by identifying the food system and water content y as input parameters. From these, computations can be made to obtain an enthalpy value at any given temperature or to plot the enthalpy curve. The following provide the sequential use of equations described above. Objectives General characterization: Hf Tf Enthalpy above Tf: H = H, + C(T-T,) Enthalpy below Tf: Coefficient a Coefficient b Enthalpy Meat Eq. (8) Eq. (9) Eq. (7) Eq. (3)
h.(4) 24

b
21

Vegetables & Fruits Eq. (8) Eq. (10) Eq. (7) Eq. (5) Eq. (6) Eq. (1)

Juices Eq. (8) Eq. (11) Eq. (7) Eq. (5) Eq. (6) Eq. (1)
1e

15 12
Fig. 4-Correlarion

.25
parameters

.28

.31

.34

.37

Eq. (1)

a vs b :

These equations can be conveniently programmed into a TI-59 calculator with two magnetic record cards, one for program and the other for constants in equations. With these portable facilities, one can conveniently compute the enthalpy difference between two temperature levels for any one of three food groups described here. Figures 8 and 9 show comparison between the literature values and those computed from these equations.

ICE FRACTIONS FROZENFOODS IN

ICE FRACTION is important in simulation computations of freezing as it affects the thermal conductivity of the frozen phase. The enthalpy balance equation of thawing a frozen specimen at T to Tf can be written as Eq (12). Since the freezing temperatures ranges 2 or less OK below the freezing temperature of water, h, latent heat of fusion of -Continued on next page water, at 273.15 was used. K
3% .

f
160 -

A meat

A meats
l

vegetables,fruits a juices

3c&~
Fig. 3-Correlarion paramerer a vs water fraction. Fig. 5-Enthalpy

.75

.80
point

.85

.90

.q

at freezing

vs water fracrion.

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46 (1981/-JOURNAL

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SCIENCE-1495

Hf-H = w C,(Tf-T) + (l-w) (X[ X+C, (Tf-T)] + (1 -X) (Tf-T)}

DISCUSSION

(12)

By using X = 3.334 x lo5 and Ci = 2.01 (Keenan and Keyes, 1936) in the above equation, the ice fraction may thus be calculated. Figures 1 and 2 show the comparison between literature values (Dickerson, 1968) and those from Eq (12).
32273 ----_

EVEN THOUGH the varieties of foods are large, their general structures have many similarities. The meat group consists of beef, chicken and fish which exhibit more oriented fiber cells structure with a relatively small amount 4.2WA meats l vegetables, 0 juices

fruits

A meats l vegetables, 0 juices

31.

fruits

BO-

.95.

y3.8B

272

> t-9 3-b

0

3-4J 271 28, .70 P .85

.8$___, .70
capacity

.75
of nonfrozen

.80
food

35
fraction.

-90

.!

.75
temperatur

.80
vs water

y
fraction.

Fig. 7-Heat

KS water

Fig. d-freezing

0 Data 3

3,

0 Data -Calculated

Calculated

2
2

cn
0) s v) 0 1

r VI
0

-1.

O0
-40
I

1 I I I

I 0 OF

I -20
I

I
I

I 1 0 OF
I

I 20

I
I .

I
4c

-20
I

20
I I I I

40
I

240
Fig. B-Calculated

250
enthalpy of beef.

I 260

270

I 280

240
Fig. 9-Calculated

250

260

270

280

en thalp y of onion

vs data.

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CORRELATION

OF ENTHALPIES

OF FOOD SYSTEMS..

of fluid between. The vegetable and fruit group has a nonoriented matrix of cells having a large moisture fraction. The juice group consists of crushed cells mixed with the fluid. These differences in structure and chemical composition would affect the mobility of water in freezing. This may result in the grouping effect as shown in Figures 3, 4, and 7. As common to all correlations, equations are reliable only within the limits of data base used. Since the present correlations are based on the data (Dickerson, 1968) with the water fraction 0.70-0.95, partially dehydrated or concentrated foods with a water fraction below 0.70 are not included. However, within this range, any synthetic foods or mixtures may use this correlation. For example, the freezing of a pre-packaged convenience food may be estimated by calculating the enthalpy change of each constituent group and sum up these groups according to mass fraction ccntribution. A comparison of 17 correlated enthalpy values and data over a temperature range233.2 (-40 K F) to 277.6 K (40 for each species indicates that the averages of abF) solute errors of meat, fruits/vegetables, and juices groups are respectively 3954, 10467, 7489 (or 1.7, 4.5,3.2 Btu/lb). These correspond to l-2% of enthalpies at 277.6 K. Probably the most interesting aspect of this study is that these correlations indicate that one needs only two input parameters to estimate the refrigeration load of foods, i.e. the water fraction and identity of one of three food groups. Identity of food group is a visual observation and the measurement of water fraction is often simple. Therefore, these correlations especially with the aid of a programmable calculator can provide the freezing heat load information readily.
CONCLUSION

systems with a water fraction larger than 0.70. The required input information is water fraction and the identity of food as one of three groups: meat, vegetable/fruit, or juice.
SYMBOLS

a,b g T W X Y X -

Correlation parameters in Eq (1) Heat capacity, J/kg.K Enthalpy, J/k% Temperature, K Fraction of solids Ice fraction Fraction of total water in food Latent heat of fusion at 273.15 J/kg K,

Subscripts f - At freezing temperature - Of ice i r - Reduced or dimensionless parameter - Of solid S

REFERENCES
Chang. H.D. 1977. MS. thesis, Dept. of Chemical Engineering. Univ. of Nebraska, Lincoln. Dickerson, R.W. Jr. 1969. Thermal properties of foods. In Freezing Preservation of Foods, 4th ed. Avi Pub. Company, Westport, CT. Joshi, C. and Tao, L.C. 1974. A numerical method of simulating the axisymmetrical freezing of food systems. J. Food Sci. 39: 623. Keenan, J.H. and Keyes, F.G.. 1936. Thermodynamic Properties of Steam. John Wiley, New York, NY. Riedel, L. 1951. The refrigerating effect required to freeze fruits and vegetables. Refrig. Eng. 59: 670. Woodrich, W.R. 1966. Specific and latent heat of foods in the freezing zone, ASHRAE J. 8: 43. Ms received 7/26/80: revised 11/12/80: accepted 3/12/81.

A SET of simple correlation equation was developed to facilitate the computation of enthalpy changes of food

YEAST CELL WALL GLLJCAN IN FOODS.

. . From page 1492 REFERENCES

Anon. 1974. Federal Register 39: 34186. Ast. H.J. 1963. Inadvertent isomerlzation of polyunsaturated acids during ester preparation. Anal. Chem. 35: 1539. Kitamura. K.. Kaneko, T.. and Yamamoto. Y. 1972. Lysis of viable yeast cells by enzymes of Arthrobacter luteus. 1. Isolation of lytic strain and studies on its lytic activity. J. Gen. Appl. Microbial. 18: 57. Kitamura, K.. Kaneko, T.. and Yamamoto. Y. 1974. Lysis of viable yeast cells by enzymes of Arthrobacter luteus. 2. Purification and properties of an enzyme. Zymolyase. which lyses viable yeast cells. J. Gen. Appl. Microbial. 20: 323. Robbins. E.A. and Seeley, R.D. 1978. Process for Manufacture of Yeast Glycan. U.S. Patent 4.122.196. Seeley, R.D. 1977. Fractionation and utilization of baker yeast. s Master Brewers Assoc. of Amer. Technical Quarterly 14(l): 35. Seeley, R.D., Robblns. E.A.. Sucher, R.W.. Schuldt. E.H., Newell, J.A., Sidoti. D.R.. and Clayton, R.A. 1974. Protein isolates from bakers yeast. Proc. 4th Int. Congr. Food Sci. & Technol. 5: 135. Sidoti. D.R.. Landgraf. G.M.. and Khalifa. R.A. 1973. The functional properties of baker yeast glycan. Presented at the 33rd Annual s Meeting of the Institute of Food Technologists, Miami, FL, June 10-14. Spiro, R.G. 1966. Analysis of sugars found in glycoproteins. In Methods in Enzymology, Ed. E.F. Neufeld and V. Ginsberg, Vol. 8, p. 3. Academic Press, New York. Sucher, R.W., Robbins, E.A.. Sidoti. D.R.. Schuldt. E.H.. and Seeley, R.D. 1975. Yeast glycan and process of making same. U.S. Patent 3.867.554. M S received 9/29/80:revlsed 4/12/81. accepted 4115181.

8%, respectively) over that found with the control sample (glycan in buffer with no other compound added) in a 1 day digest. The inhibition was more apparent after a 7 day digestion with the first lot and very evident after a 14 day digestion with the second lot (where Pioneer blend/ glycan showed 6% inhibition and GMS/gJycan showed 12% inhibition). These latter results indicate that lipid-like compounds may mask the yeast cell wall surface through hydrophobic interaction and thus prevent a full interaction of the enzyme with substrate. In a Zymolyase digestion of a normal glycan substrate, the reaction will proceed towards an end point, whereas in an inhibited reaction, some substrate will remain unavailable for hydrolysis. The longer the reactions proceed, the greater the discrepancy will be where all conditions are the same, except for the substrate inhibition factor. This hypothesis is also consistent with the results obtained in frozen dessert B-4 or 17-7 where lower glycan values were obtained with a 7 day digestion than with a l-day digestion of the same sample. Saponification of these lipid-like compounds by methanolic KOH allows solubilization of fatty acids to occur and their removal during washing. Experimentally determined glycan contents in frozen desserts pretreated in this manner gave values close to the levels reported present in these products.

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