Physico-chemical Properties of milk

Dr. M. Ashraf Paul prof / Chief Scientist

Division of Livestock Products Technology Faculty of Veterinary Sciences & Animal Husbandry SKUAST-Kashmir

Headings to be covered: Significance Acid –Base Equilibira Oxidation- Reduction Potential Density Viscosity Surface and interfacial tension Freezing Point Electrical conductivity Heat capacity and thermal conductivity Refractive Index Light absorption & Scattering

Significance:
Design

of Dairy equipments e.g. heat conductivity and viscosity etc. Determination of concentration of one or more components e.g. Sp. gr. to estimate SNF or FP to estimate added water Assessment of a chemical or a physical change e.g. TA to follow microbial activity or viscosity to assess aggregation of protein micelles or fat globules.

Advantages Speed Simplicity Potentiality for automation

Acid –Base equilibrium:

Milk contains a large # of substances which act either as weak acids or as weak bases. As a result the pH of milk is very stable. It takes quite a large dose of acid or a base to produce any appreciable change in the pH. A solution with this characteristic is called buffer solution. This buffering effect is a result of the electrical properties of substances such as proteins, phosphates, CO2, HCO3 and citrates.

Taking proteins as an example to explain the effect: Each amino acid in a protein contains a basic NH+ group and an acid carboxyl group (COOH-).  If the protein is present in sour (acid) milk with a pH < 6.7, the solution contains an excess of H+ ions or protons. These combine with the NH group in the a.a (to form NH3+).  The #of free H+ in the milk, therefore, do not increase & pH remains constant

If

the protein is present in basic milk instead, the COOH- groups will release H+ ions (forming COO groups) in the protein. Here again, pH of milk remains constant.  The more base is added the more H+ are released.  Other substances in the milk have a similar property of being able to absorb or release ions, thereby counteracting the changes in the pH of milk. The pH of milk @ 250C is 6.6(6.5-6.7) & TA=0.17% The pH of milk exhibits great temp. dependence, therefore, pH measurements should be made under controlled temp. conditions.

This

temp. dependence is attributable to insolubilization of calcium phosphate as the temperature is raised and its solution as temperature is lowered. pH decreases by about 0.01 units / 0C in milk between 10 & 300C . There could be differences in pH and buffering capacity among various lots of milk which are due to the compositional variations.  The pH is lower (6.0) in colostrums & higher (7.5) in mastitis milk. Max. buffering capacity is observed at pH between 5 & 6 and lower at a pH around 8.3 (phenolphthalein end point-practicality for determination of T.A).

Processing Effects: Moderate heating (pasteurization)- small shifts in pH and buffering by CO2 expulsion and pption of calcium phosphate with the release of H+ ions. Drastic heat treatment e.g., sterilization produces acids by degradation of lactose. The rate is slow upto 90oc and increases there after markedly. Concentration of milk lowers pH. In slow freeing pH falls as low as 5.8 ; In fast freezing there is little change. Frozen storage (-70C or -120C)  6.0  increased gradually thereafter. Effect of freezing and frozen storage are a result of insolubilization of salt constituents

Oxidation –Reduction Equilibria:  Similar to buffer action in Acid base equilibria in milk, there exists a phenomenon known as “Poising” which exhibits resistance to change of potential when the conc. of oxidant and redundant are close to equal.  Posing differs with individuals and among lots  Highest poising effect is seen in early location milk.  Fresh milk exhibits a potential of + 0.20 to + 0.30 V at noble metal electrodes.  The dissolved oxygen plays a major role. Milk drawn anaerobically from the udder reduces Methylene blue (MB), indicating that its potential is more negative then that of MB

When such a milk is exposed to oxygen, its potential is shifted towards positive side, compared to MB. Washing O2 contg. milk with O2 free gas or allowing str. lactis or lactobacilli to grow to removed free O2 from the milk causes the potential to change in negative direction conversely bubbling air or O2 through these milks will restore the positive potential. Ascorbate, lactate & riboflavin are the principal constituents responsible for Eh in O2 free milk and participate in the stabilization of Eh in O2 contg. milk.

 

The lactate-pyruate system is irreversible and activated by enzymes and mediators of a highly negative normal potential. Its presence is so minute that even if it were activated, its effect could be only very slight. Riboflavin system is an active reversible and of highly negative normal potential. Its effect is also very slight because: Its conc. is low Present in oxidized form in fresh milk

Ascorboate-Dehydroascorbate system is the principal System stabilizing the potential of O2 - free milk at a value near o.o volts and of O2 - containing milk in the zone of + 0.20 to + 0.30 volts.

Rapid change of potential as shown in the graph occurs after the dissolved O2 has been consumed by the bacteria and may be identified by the change of colour of certain dyes added to milk. The reduction time of these oxidant dyes is roughly proportional to the number of bacteria hence an index of bacterial contamination (MBRT Basis)

Effects of processing (heat treatment) on Eh.
~A sharp decrease in Eh leads to liberation of SH groups by denaturation of proteins ( ß-lg) ~ Minimum potentials are attainable by deaeration and HTST heat treatment ~ Such treatments produce dried milks of superior stability against oxidative flavour deterioration.

Density:
The density of milk is the resultant of the densities of its components complicated by variation in the ratio of solid to liquid fat and in the degree of hydration of proteins . Density of given milk specimens depends on:  Composition  Temperature  Previous history of temp. fluctuations and processing treatments.

Significance: Used in conjunction with fat test for estimating TS content. Many equations have been arrived at e.g. T=AF+BD [T=T.S;F= Fat; D= density ;A&B= coefficients of variation (CV)] Variations in composition of fat and in the proportions of lactose, proteins and salts influence the equations much less then do the variations due to physical state of the fat(Milk fat has high coefficient of expansion and it contracts on solidification.)

Methods of measurement 1. Pycnometer (weighing a given volume) 2. Hydrometer/Lactometer/series of beads of graded densities (determine the extent to which an object sinks) 3. Hydrostatic weighing of an immersed bulb e.g. Westphal or analytical balance 4. Measuring the volume of a given weight of a product e.g. dilatometer 5. Measuring the distance that a drop of product falls in a density gradient column.

The choice of method demands that a balance be struck between precision on the one hand and speed and convenience on the other.
Values of sp.gr.of milk at 15.50 C range from 1.025-1.030 (1.027); Skim milk - 1.036; Evaporated whole milk-1.066

The variation with regard to breed exists. The density of milk decrease upon increase in temperature,therefore, Temperature control is an important pre requisite to density measurements and factors for converting readings at one temperature to another should be applied. Densities of skim milk and whole milk decrease from the max. at – 5.20 C to a min. at about + 400 C

Absolute density as well as sp.gr (density relative to water) decrease from 10 to 450C (0.00005/0C). Above 400 C the absolute density decreases but sp. gr. remains virtually constant.

Processing effects
There is a small increase in density of  Homogenized whole milk at 200 C (0.000065) but no change in skim milk.  Sterilization of whole/ skim milk (1 hr / 950 C) – small decrease (0.00094) – Variations in results are considerable hence net effect negligible.  Concentrated products – observable change in densities

Viscosity: • The unit of viscosity, the Poise, is defined as the force in dynes/cm2 required to maintain a relative velocity of 1cm/sec. between two parallel planes 1 cm apart. • Fluidity (ф) is the reciprocal of viscosity. The unit used for milk is the centipoise(10-2 poise) • The viscosity may be defined by the following equation : η= F/(dv / dx )
Where η = coefficient of velocity; F = Force in dynes cm-2 necessary to maintain a unit velocity gradient between two parallel planes separated by unit distance, Dv/dx = velocity gradient in sec-1 perpendicular to the planes.

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• • • • •
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While dealing with solutions and colloidal dispersions: Kinetic viscosity γ = η / d (viscosity / density) Relative viscosity η rel = η solution / η solvent Specific viscosity η sp = η rel – 1 Reduced viscosity = η sp / c ( c = conc. of solute) Intrinsic viscosity [η ] = lim (η sp /c)
c 0

Newtonian Fluids:
Fluids for which the viscosity coefficient η depends only on T& P and are independent of rate of shear are called “Newtonian”- e.g. gasses, pure liquids, low mol. wt. solutions etc. Skim milk and whole milkNewtonian behavior; cream , concentrated milks, butter, cheese exhibit non- Newtonian behavior.

Viscometers:

• •

Coaxial cylinders: e.g. Brook field, collette, Mc Michael Falling spheres: e.g. Hoeppler Capillary tubes : e.g. Ostwald Mobilometer: features of both coaxial & falling spheres used to measure viscosity of evaporated milks

viscosity of milk and milk products depends on:
• • •

Temperature Extent of the state of dispersion of solids pH – initial followed by (initial swelling followed by disintegration).

Representative values at 200C.


Whole milk – 2.0 c.p Skim milk – 1.5 c.p Whey – 1.2 c. p

Salient contributors:
  

Caseinate micelles Fat globules Lactose has inverse effect

Effect of processing:  Heating (650C) – transient decrease in viscosity due to changes in caseins.  Concentration – increased viscosity  Homogenization – increased viscosity

Surface and interfacial Tension:
Area of contact between two phases – “interface” • if one phase is gaseous -- “surface” Surface Tension is the work required to extend the surface by unit area or force required per unit length expressed as ergs cm-2 or dynes cm-1 symbolized by γ.  In milk the important interfaces are those between liquid product and air and between the milk plasma and the fact globule contained therein

Significance of studying ST:


• •

Ascertaining the relative effectiveness of milk components as depressants To follow the changes in surface active components as a result of processing. To monitor release of FFA during lipolysis Understanding foaming characteristics of milk

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Method of measurement

Dynamic: applicable in freshly formed surfaces  Static: provided majority of information on milk so far  Studies reveal that the orientation in surface in milk are so rapid that values of dynamic method equaled the static, therefore are sparsely discernible during the time intervals involved in dairy processing. Five principal static procedures for the measurement of ST involve determination of: 1) Height of rise of liquid in a capillary 2) Weight or volume of drops formed by liquid flowing from a capillary tip (sometime considered as semi-dynamic) 3) Force required to pull a ring or plate out of a surface (most widely employed) 4) Maximum pressure required to force a bubble of gas through a nozzle immersed in liquid 5) Shape of a pendant drop hanging from a capillary

Apparatus employing tension balances are also available (Du Nouy balances) Surface tension of milk is of the order of 50 dynes cm-1 at 200C compared to water 72.75 dynes cm-1 at 200 C. The principal surface active components of milk: ~ ~Proteins ~ ~Milk fat ~ ~Phospholipids ~ ~FFA Powerful depressants of tension include: Casein, Lactalbumin, Lactglobulin, BSA and 1g are less so. Rennet whey has nearly same ST as that of milk

The protein and protein–PL complex of FGM are significant depressant i.e. why the ST of whole milk lies a few dynes lower than skim milk. o Fat content : ST decrease with increasing fat content upto 4% fat thereafter there is no decline; the protein–PL complex is responsible for very low surface tension of sweet cream buttermilk. o Temperature raised in the range of 10-600C – ST ST of milk (at 50C brought to 200C) lower than milk cooled to 200 C ; SM separated at 600C – ST (than) SM Separated at 50 C– ST Apparently surface active substance are released from fat globules at low temp

Lipolysis: FFA released depress ST of milk. Short chain FA rancid flavour Long Chain FA ST depressant. o Homogenization: Raw milk homogenization lipolysis low ST Pasteurized milk homogenization ST o Heat Treatment: Little effect Sterilization denaturation & coagulation of proteins proteins no longer effective Surface active agents ST
o

Freezing point
The freezing point of milk depends upon the concentration of water– soluble components. Objective: Determination of water content of the product in order to detect the illegal addition of water (FP of authentic bovine milk varies within narrow limits). Determinants: Major constituent of low MW .g.Lactose,salts FP is nearly independent of variations in the conc. of proteins, fat etc. There is furthermore a complementary relationship between lactose and Nacl in milk such that the osmotic pressure and hence the FP is maintained within a narrow range

Methods: o Hortvet method (1921)universally accepted official method-modifications have been made over the time such as replacing either cooling system with mechanical refrigeration; addition of mechanical stirring and tapping devices; employing thermistors in place of mercury-in- glass thermometers etc. o The latter cryoscopes became popular because of speed and ease of operation. o These measuring procedures involve measurement of the difference between the FP of a standard sol. and FP of milk- the errors, if any get reflected in both observed values and thus be eliminated. FP calibration standard solutions: ~Sucrose-poor reproducibility; rapid microbial decomposition ~Nacl-comparable results with sucrose sol., stable for long time

Factors affecting FP: ~ Season, feed water intake, stage of lactation, breed of cow and time of the day (morning vs. evening milk) ~ Microbial decomposition - production of lactic acid  lower FP ~ Storing milk at lower temp. or freezing  increased FP ~ Heating  increased FP ~ Vacuum treatment  Co 2 removal  increased FP
In 1970 AOAC adopted an officinal interpretation which specified that milk with a FP of – 0.525 0 C or below may be presumed to be water free

Electrical conductivity
EC of milk has been considered as a possible index of : ~ ~Mastitis infection ~ ~Added water ~ ~Added neutralizers ~ ~As a means of controlling solids concentration and composition in dairy processing ~ The specific conductance of cows milk reflects its concentration and activity of ions & is of the order of 0.005 S /cm. or 5mS/cm at 250C – ( range0.0040 -0.0055 S cm-1 or 4 - 5.5 mS cm-1)

•Higher values represent Mastitis infection which increase the concentration of sodium and chloride in milk. •Temp control is important in the measurement, since the conductivity increases by about 0.0001 units/ 0 C rise in temp. •No significant relationship between viscosity and conductivity, however reduction in viscosity allows for a greater ionic mobility hence increased conductivity. •Na, K, Cl ions of milk – greatest contributes, since they are present in in highest concentration.

There is no significant difference between cow and buffalo milk conductivity however adulteration of buffalo milk with cow milk causes a detectable change in EC. The fat globules of milk reduce the conductivity by occupying the volume and by impeding ion mobility thus the conductivity of whole milk is less than the conductivity of SM and that of cream varies with the fat content . Homogenization has no measurable influence. The conductivity of whey and ultrafiltrate is slightly higher than SM.

Evaporated and concentrated infant milk products  having poor physical stability  lower conductivity compared to more stable products.  Increased acidity leads to increased conductivity  Concentration up to 28% solids  increased conductivity, thereafter there is a decrease. Direct conductivity measurements do not provide a satisfactory index of added water in milk . However, measurements of conductivity in non- aqueous solvent can be useful in detecting adulteration

Heat capacity

 

Heat capacity is the quantity to heat required to raise the temp of a unit mass through a unit range, expressed in terms of Cal g-1 0 C-1 . The term specific heat is interchangeably used with heat capacity & is determined with the help of calorimeter. The energy input and resultant temp. rise both are measured. Skim milk exhibits a small but definite linear increase in heat capacity between 0-500C from about 0.933 to 0.954 Cal g-1 0 C-1 . Heat capacity decreases with the increase in T.S content of the sample. Dried skim milk products’ heat capacity = 0.28 to 0.32 Calg-1 0 C-1 in the 18 to 300 C temp. range. Heat capacity of milk fat = 0.52 Cal g-1 oC-1 . The heat capacity of milk and cream depends on the fat content.

Thermal conductivity
Thermal conductivity is the rate of heat transfer by conduction through unit thickness across unit area of substance for a unit difference of temp.

λ = Q d / At(T2 – T1)
Where, Q= Amt of heat transferred through the sample. A= Area d = Thickness t = time T2 - T-1 = temp difference
λ water 0–100 0C =0.48-0.58 Kcal/m/hr/ 0C λ Milk @ 37 0C =0.46Kcal/m/hr/ 0C λ Milk @ 80 0 C =0.53Kcal/m/hr/ 0C
We may assume

λ Decreases with the increase in TS & fat Determinants of λ of dried milk products:  ~ Bulk density  ~ Composition

a linear increase in λ from 0 - 100 0C in milk

Refractive Index :
It is the ratio of the speed of light in a vacuum to its speed in that substance. Measurements of bending of light gives a direct measure of RI, n. Specifically n = sin I / sin r ( i= angle of incidence ; r = angle of refraction )  RI varies with  ~Sample temp ~Wave length of light  Used as a means of determining total solids or added H2 0 in milk thus n D20 refers to index at 200C with D line of the sodium spectrum (589.0 and 589.6mm) • RI water n D20 = 1.33299 • Cow milk = 1.3440-1.3485 • Buffalo = 1.3440-1.3485 • Goat, ewe, human= higher than above • Milk fat = 1.4537 to 1.4552 at 400 C

Abbe Refractometer: Is used to determine the RI in milk which employs a thin layer of film Fat has no contribution to RI of whole milk because refraction occurs at the interface of air & continuous phase. Sterilization & subsequent storage does not alter RI.

Light Absorption & scattering:
Milk is a colloidal dispersion of proteins and an emulsion of fat in an aqueous solution of salts and other compounds , thus it not only absorbs light at many λ because of large # of compounds present but also scatters it as a result of the presence of particles of various sizes. Water strongly absorbs IR radiation, therefore, milk is opaque to a major portion of this region. Light absorption , scattering - basis for direct analysis of milk (largely quantitative) Advantages of spectrophotometric techniques; • Speed • simplicity • capability for automation

Light absorption :
Examples: IRMA – method for determination of fat, protein & lactose in milk based on absorption of IR energy at specific λ . The difference in absorbance of a homogenized milk sample and pure water is measured at 5.8,6.5 and 9.6 μ for fat, Protein and lactose respectively. Method correlates well with the chemical methods with a caution of proper calibration and operation. .

Light scatting:
Both fat and proteins of milk scatter light, the amount of scatting depends upon: No size of particles  λ of incident radiation Difference in RI of different kinds of particles and solvent. Examples: ~Milkotester Homogenization EDTA dilution . Utilizes white light in a special photometric system to determine attenuation due to scattering and thus the fat content of milk. Method compares favorably with traditional methods provided proper caliberation and operation is carried out .

~The dye binding methods for meaniring protein in milk. Milk + sulfonic acid dyes  complex formation with basic amino acid residues of milk protein at low pH Correlates well with Kjeldhal method

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