NT20903 Food Chemistry and Biochemistry Academic Session 2011/2012

Week 1: Water Chemistry (Part I) Properties, Solutes Interactions & Types of Water
Mohd Nazri Abdul Rahman BFoodSc. (Hons) (UMS), MSc. (UKM)
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Chapter Objectives
At the end of this chapter, you will be able to:
1. Understand the nature and properties of water and aqueous solutions. 2. Identify the types of water in food systems 3. Consider many roles played by water in food systems 4. Understand the central role of water in food chemistry. 5. Discuss the important of water activity in prolonging of food shelf life
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Water

Most abundant compound found on earth, food component that is given less attention. Major chemical component of the earths surface. Is the primary solvent in which metabolic/life processes. Only liquid that most organisms ever encounter.

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Water
Organisms are 70 90% water. Normal metabolic activity can occur only when cells are at least 65% H2O. All food contains water (water content varies in food) a substantial component of most foods composition. % Water E.g. No. Food Type
1. 2.
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Water
Dependency of life on H2O is not a simple matter, but it can be grasped by considering the unusual chemical and physical properties of H2O.

Water & its ionization pcdts, H+ ions and hydroxide ions, are critical determinants of the structure & function of many biomolecules, including AAs & CHONs, nucleotides & nucleic acids, & even phospholipids & membranes.
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Water
Water is an indirect participant a difference in the conc. of H+ ions on opposite sides of a membrane represents an energized condition essential to biological mechanisms of energy transformation.

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Water
A molecule consist of 2 atoms of hydrogen and 1 atom of oxygen (H2O) which is chemically bonded on covalent.
O
Covalent bond

H2O
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Water
A unique molecule because H2O has polar bonds, has unequal distributions of +ve and -ve charges. Water molecules are dipoles (dwikutub).

OH+
Dipoles
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H+

Water
Every molecule bonds to another forming a hydrogen bonds (strong attractive forces among molecules). OOHydrogen bond H+ OH+ O1/13/2013 NT20903 Food Chemistry & Biochemistry

H+

O-

H+

H+

Importance of water in life

1. As a reactant and reaction medium, has solvent properties. 2. Stabilizes many biopolymer conformations. 3. Facilitation of dynamic behavior of macromolecules. 4. Catalystic (enzymatic) properties. 5. Carries nutrients and waste materials. 6. Stabilize / governs / maintain body temperature.
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Water Has Unusual Properties

Compare water with chemical cpds of similar atomic organization & molecular size such as hydride of oxygen, with hydrides of oxygens nearest neighbors in the periodic table, namely, ammonia (NH3) and hydrogen fluoride (HF), or with the hydride of its nearest congener, sulfur (H2S).

Water has a substantially higher boiling point, melting point, heat of vaporization, & surface tension.
Suggest that intermolecular forces of attraction between H2O molecules are high. Thus, the internal cohesion of this substance is high.

Water has an unusually high dielectric constant, its maximum density is found in the liquid (not the solid) state, and it has a negative volume of melting (that is, the solid form, ice, occupies more space than does the liquid form, water). Food Chemistry & Biochemistry 1/13/2013 NT20903 11

Physical Properties of H2O

Waters ability to engage in 3-dimensional H+ bonding unusual properties:
High melting and boiling point Surface tension and enthalpies of various phase transitions (extra energy to break internal H+ bonds)

Covalent bond Hydrogen bond

Boiling point was broken the only hydrogen, not the covalent bond.
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Physical Properties of H2O

On the basis of comparison waters properties with those of molecules of similar MW & atomic composition (CH4, NH3, H2S, H2Se, and HF), water is seen;
1. To have unusually high melting and boiling point temperatures 2. To exhibit unusually large value for surface energy, permittivity (dielectric constant), heat capacity, heats of phase transformation (fusion = pelakuran, vaporization = pengewapan, and sublimation = pemejalwapan) 3. To have a somewhat lower than expected density 4. To exhibit the unusual property of expansion upon solidification 5. To have a viscosity that is quite normal
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Table 1.1 Physical Properties of Water and Ice

Property Molecular weight Melting point (at 101.3 kPa) Boiling point (at 101.3 kPa) Critical temperature Critical pressure Value 18.0153 0.00C 100.00C 373.99C 22.064 Mpa

Triple point temperature

Triple point pressure

0.01C
611.73 Pa

Hvap at 100C (haba pengewapan)

Hsub at 0C (haba pemejalwapan)

40.647 kJ/mol
50.91 kJ/mol
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Hfus at 0C (haba pelakuran) Food Chemistry & Biochemistry 6.002 kJ/mol 1/13/2013 NT20903

Table 1.2 Properties of Related Small Molecules

CH4 NH3 H2O H2S H2Se HF

MW 16.04 mp (C) - 182.6 bp (C) - 161.4 Hvap 8.16 (kJ/mol)

17.0 - 77.7 - 33.3 23.26

18.01 0 100 40.71

34.08 -86 -61 18.66

80.9 -60 - 41

20.01 - 83.1 19.5

Sebatian ini boleh dibandingkan dgn air krn kesemuanya mempunyai proton (+ve) yg terikat kpd oksigen atau bbrpa atom elektronegatif yg lain. Ini dpt dilihat, H2O mempunyai;
Takat didih paling tinggi Haba tentu pengewapan yg paling tinggi Takat lebur paling tinggi
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a. Thermal Conductivity (TC)

Thermal conductivity of H2O is large as compared with most other liquids. Thermal conductivity of ice is larger than might be expected for a nonmetallic solid. Thermal conductivity of ice at 0C is approximately quadruple that of liquid H2O at the same T, indicating that ice will conduct thermal energy at a much greater rate than will immobilized (e.g., tissue) water. Since the heat capacity of H2O is approximately 2x that of ice, the thermal diffusivities of H2O and ice differ by about a factor of 9.
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b. Thermal Diffusivity (TD)

Since TD is indicative of the rate at which a material will undergo a change in T, we would expect that ice, in a given thermal environment, will undergo T change at a rate 9x greater than that for liquid H2O. These differences in TD & diffusivity values for H2O and ice provide a good basis for u/standing why tissues freeze more rapidly than they thaw under symmetrically applied T differentials.
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Hydrogen Bonding in Water Is Key to Its Properties

2 hydrogen atoms of water are linked covalently to oxygen, each sharing an electron pair, to give a nonlinear arrangement.

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 This bent structure of the H2O molecule has enormous influence on its properties. If H2O were linear, it would be a nonpolar substance. In the bent configuration, however, the electronegative O atom and the two H atoms form a dipole that renders the molecule distinctly polar. Furthermore, this structure is ideally suited to H-bond formation. Water can serve as both and H donor and an H acceptor in H-bond formation.
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 The potential to form four H bonds per water molecule is the source of the strong intermolecular attractions that endow this substance with its anomalously high bp, mp, heat of vap., & surface tension.

In ordinary ice, the common crystalline form of water, each H2O molecule has four nearest neighbors to which it is hydrogen bonded: Each H atom donates and H bond to the O of a neighbor, and the O atom serves as an H-bond acceptor form H atoms bound to two diff. water molecules results a local tetrahedral symmetry (figure below).
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Structure of normal ice (hexagonal ice six H-bonded molecules)

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 Hydrogen bonding in water is cooperative.

an H-bonded water molecule serving as an acceptor is a better H-bond donor than an unbonded molecule (and an H2O molecule serving as an H-bond donor becomes a better H-bond acceptor).

Thus, participation in H bonding by H2O molecules is a phenomenon of mutual reinforcement. The H bonds between neighboring molecules are weak (23 kJ/mol each) relative situated asymmetrically between the two oxygen atoms along the O-O axis. There is never any ambiguity about which O atom the H atom is chemically bound to, nor to which O it is H bonded.
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Structure of Ice Is Based on H-Bond Formation

In ice, the hydrogen bonds form a space-filling, 3D network. These bonds are: directional and straight; that is, the H atom lies on a direct line bet. the two O atoms. This linearity & directionality mean that the H bonds in ice are strong. Directional preference of the H bonds leads to an open lattice structure. Example: if the water molecules are approximated as rigid spheres centered at the positions of the O atoms in the lattice, then the observed density of ice is actually only 57% of that expected for a tightly packed arrangement of such spheres.
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 The H bonds in ice hold the water molecules apart.

Melting involves breaking some of the H bonds that maintain the crystal structure of ice so that the molecules of water (now liquid) can actually pack closer together. Thus, the density of ice is slightly less than that of water. Ice floats, a property of great importance to aquatic organism in cold climates.
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 In liquid water, the rigidity of ice is replaced by fluidity and the crystalline periodicity of ice gives way to spatial homogeneity.
The H2O molecules in liquid water form a disordered H-bonded network, with each molecule having an average of 4.4 close neighbors situated within a center-to-center distance of 0.284 nm (2.84 A). At least half of the hydrogen bonds have nonideal orientation (that is, they are not perfectly straight); consequently, liquid H2O lacks the regular latticelike structure of ice.
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Molecular Interactions in Liquid Water Are Based on H Bonds

The participation of each water molecules in an average state of H bonding to its neighbors means that each molecule is connected to every other in a fluid network of H bonds. The average lifetime of an H-bonded connection between two H2O molecules in water is 9.5 psec (picoseconds, where 1 psec = 10-12 sec). Thus, about every 10psec, the average H2O molecule moves, reorients, and interacts with new neighbors (figure @ right side).
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Solvent Properties of Water Derive from Its Polar Nature

Because of its highly polar nature, water is an excellent solvent for:
ionic substance such as salts; nonionic but polar substances such as sugars, simple alcohols, and amine; and carbonyl-containing molecules such as aldehydes and ketones.

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Example: Sodium chloride is dissolved because dipolar water molecules participate in strong electrostatic interactions with the Na+ and Cl- ions, leading to the formation of hydration shells surrounding these ions.
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Water Solute Interactions

1. Macroscopic level
Water binding and hydration Water holding capacity (WHC)

2. Molecular level
Interaction with;
a) Ions and ionic group b) Neutral groups (hydrophilic solutes) c) Non-polar substances

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1. Macroscopic Level
a) Water binding and hydration = tendency of water to associate with hydrophilic (suka air) substances. b) Water holding capacity = the ability of a matrix of molecules (macromolecules) at low come to physical entrap large amount of water in order to inhibit exudation, e.g. pectin, starch, etc. Example: Sponge = absorb more water = WHC
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 Bulk flow is restricted but movement of individual molecule is possible. WHC has profound effect on food quality:
syneresis of gel, thaw exudates, inferior performance of animal tissue due to decline in pH during post-mortem.

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2. Molecular Level
a) Interaction with ions and ionic groups Hinder mobility of water (disekat daripada bergerak); covalent bond > H2O-ion bond > H2O H2O H2O and simple inorganic ions undergo dipoleion interactions (Figure 1.1). Strongly interact with H2O molecules, causing mobile and densely packed.
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 Fig. 1.1 Likely arrangement of water molecules adjacent to sodium chloride ion pair.

Na +

Cl O

O
O
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 Fig. 1.1 Likely arrangement of water molecules adjacent to sodium chloride ion pair. Only water molecules in the plane of the 1/13/2013 paper are represented. Chemistry & Biochemistry NT20903 Food 34

 Large ion and monovalent (K+, Rb+, NH4+, Cl-, Br, NO3, etc) have weak electron field; and are not structure breakers. Disrupt the normal structure of H2O. Varying abilities to hydrate (compete for H2O), alter H2O struct. etc. Conformation of proof and stability of colloids, greatly influenced by the kings and amounts of ions present.
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b) Interactions with Neutral Groups (hydrophilic Solutes) Interaction H2O ion > H2Ononionic/hydrophilic = H2O H2O/depends on the internal strength, may or may not reduce mobility and alter other properties. Hydrogen bonding of H2O with various potentially eligible groups (e.g. hydroxyl, amino, carbonyl, amide, imino, etc.) results in water bridges where 1 H2O molecule interacts with 2 eligible H-bonding sites on 1 or > solutes.
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c) Interaction with nonpolar substances Mixing H2O with hydrophilic substances such as hydrocarbons, rare gases, and the apolar groups of fatty acids, amino acids, and CHONs is considered as thermodynamically unfavorable event (hydrophobic hydration). E.g. H2O + oil = unmixed due to nonpolar H2O tends to minimize its association with nonpolar entities that are present association.
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(a) Hydrophobic hydration = a process of reduction in entropy, considered an indicator of increased order, is thought to occur bec. of special structures in water that form in the vicinity of these incompatible apolar entities.

(b) Hydrophobic interaction = process of a partial reversal of hydrophobic hydration.

Fig. 1.2 Schematic depiction of (a) hydrophobic hydration and (b) hydrophobic association. Open circles are hydrophobic groups. Hatched areas are water.
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 Hydrophobic hydration = a process of reduction in entropy, considered an indicator of increased order, is thought to occur bec. of special structures in water that form in the vicinity of these incompatible apolar entities. Hydrophobic interaction = process of a partial reversal of hydrophobic hydration. R (hydrated) + R (hydrated) R2 (hydrated) + H2O
Where R = apolar group (Fig. 1.2b) above

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Type of Water
1. Free water (air bebas) as a solvent for spreadibility; as a medium for colloidal dispersions (agen penyebar) 2. Immobilized water (air pegun) in tissue cell (either extra- or intracellular fluids) 3. Hydrated water (air dihidratan) combines in the molecules 4. Absorbed water (air serapan) in gel. 5. Adsorbed water (air jerapan) on the surface of the solid.
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 Water also categorized into vicinal water (air visinal) and multilayer (air lapisan berbilang).
Type I (Monolayer, vicinal water) Type II (Multilayer water) Type III (Entrapped water) Type IV (Free water)

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Water Binding in Foods

Water in food and biological systems exists in 3 types or degrees of boundness. 1. Pure water with full activity can be considered as free water (Type IV) and is not found in biological systems. 2. Entrapped water or Type III water involves physically entrapped water in tissues and membranes and is similar in its properties to water in dilute solutions.
The freezing point is reduced only to a slight extent and the normal solvent capacity is exhibited by entrapped water. It is easily removed during evaporation, concentration or drying operation.
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 Type III of water constitutes the major proportion of water in plant and animal food tissues and is readily available for chemical reactions and the growth and activity of microorganisms.
As it is removed the remaining water gradually assumes a lower activity. When all the Type III water is removed the moisture content is about 12 to 25% by weight and the water activity is lowered to 0.8. The rates of chemical reactions such as sugar-amine reactions (Maillard reaction) increase as the water activity is lowered to about 0.8 and less.
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3. Multilayer water or Type II water involves water that is Hbonded in water-solute and water-water clusters, and water in micro-capillaries.
It has limited solvent capacity and does not freeze completely even at -40C. It is more difficult to remove this type of water than Type III water. Partial removal of Type II water eliminates the last possibility of microbial growth and greatly reduces most kind of chemical reactions. Complete removal of Type II water leaves 3 to 7% of moisture level in the food (water activity is about 0.25) and corresponds approximately to optimum stability of dry pcdts that contain significant amount of oxidizable lipids.
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 This small amount of water is required to inhibit oxidative rancidity through several mechanisms. The small amount of water facilitates destruction of free radicals, H-bonds to hydroperoxides and slows the rate of their conversion to other pcdts, and hydrates or coordinates with metals, thereby reducing their ability to catalyze oxidation.

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4. Monolayer, vicinal water or Type I water involves water adsorbed to solutes as a monolayer and water in chemical hydrates.
This corresponds to a moisture content in the range of 0 to 0.7% by weight and can be partially removed by dehydration but not by freezing even at -40C. Type I water is tightly bound and is considered to be true bound water. It is in this region where acceleration of lipid phase reactions (oxidative rancidity) occurs as lipids become more exposed. However, the rates of enzyme catalyzed reactions such as hydrolysis of lipids or proteins decrease.
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Fig. 1.3 shows the effect of moisture content and water activity of foods on the growth rates of m.o and of various chemical reactions that occur in foods.

It also indicates the shelf life or storage stability of foods as a function of water activity.

Fig. 1.3 Rates of chemical and enzymatic reactions and 1/13/2013 NT20903 Food Chemistry & water microbial growth as a function of Biochemistry activity in foods. 47

 Fig. 1.3 shows the effect of moisture content and water activity of foods on the growth rates of m.o and of various chemical reactions that occur in foods. It also indicates the shelf life or storage stability of foods as a function of water activity.

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 The mc-aw relationship is temp. dependent & a in At any given mc, the aw during temp. shifts the boundaries of zones and II to semula) resorptionI (erapan points of > moisture and lower aw.

(addition of water to dry sample) is less than that Water adsorption and desorption isotherms do during adsorption (jerapan) not at any given a the andcoincide, i.e. theyshown exhibit hysteresis asw content1.4 in Fig. during desorption (penyerapan) is greater than that during adsorption. Hysteresis = lack of
superimposability on an isotherm prepared by desorption.

Fig. 1.4 Hysteresis of moisture sorption isotherm (MSI).

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 At any given mc, the aw during resorption (erapan semula) (addition of water to dry sample) is less than that during adsorption (jerapan) and at any given aw the content during desorption (penyerapan) is greater than that during adsorption.

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Sifat-sifat Air Visinal & Air Lapisan Berbilang

Sifat-sifat Keterangan am Air Visinal Air yang berinteraksi kuat dengan tapak hidrofilik khusus pada juzuk bukan akueus melalui sekutuan air-ion dan air-dwikutub; apabila air jenis ini berada pada aras maksimum, air ini cukup untuk memberikan penutupan satu lapisan kumpulan yang sangat hidrofilik dan boleh sampai daripada juzuk bukan akueus; juga merangkumi air di dalam mikrokapilari (garis pusat < 0.1 NT20903 Food Chemistry & Biochemistry um) Air Lapisan Berbilang Air yang memenuhi baki tapak lapisan pertama dan membentuk beberapa lapisan tambahan di sekeliling kumpulan hidrofilik juzuk-juzuk bukan akueus; ikatan hidrogen air-air dan air-bahan larut paling banyak.

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Sifat-sifat Takat Sejuk beku dibandingkan dengan air tulen

Air Visinal Tak boleh disejuk beku pada suhu 40C (terikat)

Air Lapisan Berbilang Kebanyakannya tak boleh disejuk beku pada suhu -40C (terikat); bakinya boleh disejuk beku dengan takat penyejukbekuan yang amat direndahkan

Kemampuan pelarut Tiada

Sedikit hingga sederhana

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Sifat-sifat

Air Visinal

Kemobilan translasi Amat dikurangkan (aras molekul) dibandingkan dengan air tulen Entalpi pengewapan Amat ditingkatkan dibandingkan dengan air tulen % Air jumlah di 0.5 0.4% dalam makanan berkelembapan tinggi (90 H2O atau 9 g H2O per g jirim kering)
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Air Lapisan Berbilang Dikurangkan sedikit hingga banyak

Ditingkatkan sedikit hingga sederhana 3 2%

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Sifat-sifat Hubungan dengan isoterma erapan

Air Visinal Air di dalam zon I isoterma terdiri daripada sedikit sahaja air juzuk dengan bakinya ialah air visinal; sempadan atas zon I tidak jelas dan agak berubah-ubah mengikut hasil keluaran dan suhu

Air Lapisan Berbilang Air di dalam zon II isoterma terdiri daripada air yang terdapat di dalam zon I campur air yang ditambah atau disingkirkan di dalam kawasan zon II; air yang kedua ini semata-mata air lapisan berbilang; sempadan zon II tidak jelas dan agak berubahubah mengikut jenis makanan dan suhu
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Sifat-sifat

Air Visinal

Kesan pemerosotan Kestabilan yang biasa berlaku keseluruhan optimum pada nilai monolapisan (0.2 0.3 aw)

Air Lapisan Berbilang Apabila kandungan air meningkat melampaui bahagian bawah zon ini, kadar hampir semua jenis tindakbalas meningkat

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