KANISHKA BHUNIA WSU ID: 11260806 ASSIGNMENT 1 Raoults law and its implication in water activity Raoults law

is applicable for ideal solution or very dilute solution. A solution is said to be ideal if escaping tendency of each component in a solution is proportional to mole fraction of this component in solution. Usually, the escaping tendency is measured by the partial vapour pressure of that component. So, the Raoults law can be expressed as:

where PA is the partial vapour pressure of component A, XA is its mole fraction, and is the vapour pressure of pure liquid A at the same temperature. But the application of Raoults law in food system is not applicable because of presence of solute. If the vapour is non-ideal, at very low pressure may be replaced by fugacity. The water activity can be defined as: aw = f/f0, f is the fugacity at a temperature and f0 indicates fugacity of pure water at the same temperature. As dilution increases, the solvent in solution approaches the ideal behavior specified by Raoults law and finally it becomes:

How is pH associated with water activity in maintaining food safety? In food preservation techniques, to control microbial growth, we can reduce water activity or acidify the food material. Increasing the acidity of foods, either through fermentation or the addition of weak acids, has been used as a preservation method since ancient times. In their natural state, most foods such as meat, fish, and vegetables are slightly acidic while most fruits are moderately acidic. A few foods such as egg white are alkaline. Lowering the pH of a food increases the effectiveness of an organic acid as a preservative. It is well known that groups of microorganisms have pH optimum, minimum, and maximum for growth in foods. Another important characteristic of a food to consider when using acidity as a control mechanism is its buffering capacity. The buffering capacity of a food is its ability to resist changes in pH. Foods with a low buffering capacity will change pH quickly in response to acidic or alkaline compounds produced by microorganisms as they grow. Meats, in general, are more buffered than vegetables by virtue of their various proteins. In general, pathogens do not grow, or grow very slowly, at pH levels below 4.6; but there are exceptions. Many pathogens can survive in foods at pH levels below their growth minima. It has been reported that C. botulinum was able to produce toxin as low as pH 4.2.

Table 1. Approximate pH values permitting the growth of selected pathogens in food. Microorganism Clostridium perfringens Vibrio vulnificus Bacillus cereus Campylobacter spp. Shigella spp. Vibrio parahaemolyticus Clostridium botulinum toxin Clostridium botulinum growth Staphylococcus aureus growth Staphylococcus aureus toxin Enterohemorrhagic Escherichia coli Listeria monocytogenes Salmonella spp. Yersinia enterocolitica Sources: Table 5.3 in ICMSF 1980, p 101. So, it is noticeable that most of pathogens are able to grow at higher pH i.e. at alkaline state. But, below pH 4.2 there are few pathogens are able to sustain. Alkaline nature indicates presence of salt in medium which binds water at the same time and lowers the water activity. So, we have to have an optimum pH and water activity relationship to regulate this phenomenon. pH Values Water Activity 4.6 or less 0.92 or less >0.92-0.95 >0.95 Non PHF/ Non TCS Non PHF/ Non TCS Non PHF/ Non TCS >4.6-5.6 Non PHF/ Non TCS Non PHF/ Non TCS PA >5.6 Non PHF/ Non TCS PA PA Minimum 5.5 - 5.8 5.0 4.9 4.9 4.9 4.8 4.6 4.6 4.0 4.5 4.4 4.39 4.21 4.2 6.0 - 7.0 7.0 - 8.0 6.0 - 7.0 7.0 7.0 - 7.5 7.2 7.8 - 8.6 Optimum 7.2 7.8 6.0 -7.0 6.5 - 7.5 Maximum 8.0 - 9.0 10.2 8.8 9.0 9.3 11.0 8.5 8.5 10.0 9.6 9.0 9.4 9.5 9.6

PHF means Potentially Hazardous Food, TCS means Time/temperature control for food safety, PA means Product assessment required

The following table illustrates the relationships between pH, water activity (aw), and current low-acid and acidified regulations by USFDA. Final Equilibrium pH 4.6 4.6 >4.6 >4.6 Water Activity (aw) 0.85 >0.85 0.85 >0.85 Low Acid* Acidified** (21CFR (21CFR 108.35/113) 108.25/114) No No No Yes No Yes No No

This table does not apply to foods which are naturally or normally acid.

What is the definition of water activity in terms of partial pressure and fugacity? WaterActivity, If the solution is ideal and vapour behaves ideally, then the pressure term and fugacity term is interchangeable. Fugacity is basically the escaping tendency of vapour from food material. So, it becomes

What is Gibbs law and how does it relate to the water activity measurement at equilibrium state? The physicochemical equilibrium is determined by the equality of chemical potential of each component which is actually the partial molar free energy of each component. The chemical potential () of a component in the liquid (L) phase is equal to that in the vapor (V) phase if vapor and liquid are in equilibrium:
L = V

Then the Gibbs free energy can be expressed as:

G = H-TS

where H is the enthalpy, T is absolute temperature and S is the entropy and i = . So, it can be said that the chemical potential of a component of a homogenous mixture is equal to the ratio of the increase in Gibbs free energy on the addition of an infinitesimal amount of the substance. At constant temperature and pressure it can be written:
dG = idni

Finally, the general criterion for a system to be at equilibrium is:

dG = + =0

How does the Clausius-Clapeyron equation describe the moisture sorption isotherm at different temperatures? The Clausius-Clayperon equation is as follow:

Where t is absolute temperature, Qs is the net isosteric heat of sorption; R is the universal gas constant. Heat of sorption at low moisture content is high and as the moisture content increases, Qs value falls. So, increase in temperature at constant water activity causes decrease in water amount. At After integrating both sides at constant moisture content it becomes:

Where and are the water activities at temperature T2 and T1, respectively at a constant moisture content. So, at fixed moisture content if water activity increases, temperature also increases. In the other hand, it can be said that amount of water adsorbed usually decreases as temperature increases.