Chemical Oceano 8 128 raphy —_—— 43. Review of the Structure of Water il ic view the theories of water structure. Several reviews and mono. ie wil now ri mumarzing the statu ofresegch onthe structure of wate Ay Bap rt eurvey is given in the books edited by Franks (1986). We can divide the water exer gure models into two major categories: the uniformist, or average models and the sxture models. Both models recognize that water is a very structured liquid; the major Js is that in the mixture models the simultaneous exist. difference between the two model ence of at least two different states of water is thought to be present. 4.3.1 Uniformist (Average) Models Bernal and Fowler (1933), Pople (1951), Wall and Horning (1965), and Falk and Kell (1966) were proponents of this model. The basic element of the uniformist view is that there exists in water no local domains of structure different from that of any other arbitrarily chosen element of water. In the process of averaging, the individual water molecule behaves at any time much like any other water molecule is behaving. Bernal and Fowler's (1933) original model has been used and has worked well in many applications. Pople's (1951) treatment gave a far greater qualitative insight into the structure of water. Pople explained the maximum density of liquid water as resulting from two opposing effects— increase in volume caused by expansion of the lattice structure and a bending of the H-bonds. Thus, this model treats liquid water as an “ice like” lattice with differences caused by the bending of bonds, not the breaking of bonds. 4.3.2, Mixture Models ‘These models have received more notice over the years. We can divi : .. into the following categories: vide the mixture model Broken down ice lattice models: ice-like units in equilibrium with monomers Cluster models: H-bonded clusters in equilibrium with monomers Clathrate models: clathrate-like cages in equilibrium with monome ers, Significant structure model or Eucken’s polym« I: not necessarily a monomer Polymer model: bulky species that are Pepe In each case at least two different species of water exist — some type of structured units and a dense species such ae ae species representing popular mixture model called the flickering cluster model is shown in each siete ot Z igure 4.8, Wate monomers are thought to be in a dynamic equi it snonomers a Iynamic equilibrium with large clusters of hydrogen” 4,3.2.1Ice-Like Models Rowland (1880) was the first o suggest an equilibrium between i ‘ ec oe (1965) proposed a model in which the monomeric HO molecules sand onomer. Samoilov interstitial spaces of an “ice like” lattice (Figure 4.9). Since ice ad 15 ‘tucked away” in the Gall, 1999; Weidenfeld and Nicolson, 1999) and a number of amae ATOWN crystal phases 2003), some workers have assumed that the structured form is ite es forms (Guthrie, ‘Tamann, (1895), fot ila. ia ai MDIonic Interactions ~ Clusters FIGURE 4.8, ‘The Frank and Wen flickering cluster model for the structure of water. example, suggested that there should be as many types of structures in liquid water as there are types of ice (eg,, ice I, I, etc. [Figure 4.10]). The very careful x-ray diffraction study of Danjord and Levy (1962) was found to be in good agreement with a broken down ice structure model. They suggest that the monomeric water molecules occupy positions in the interstices of the ice. (This is similar to Samoilov’s model). Although the model has been used to successfully reproduce the x-ray data, many adjustable parameters were used; thus, there has been criticism of this model. Davis and Litovitz (1965) suggested a model involving puckered hexagonal rings similar to the ice rings formed in the basal plane of ice. Density variations are accounted for by assuming two rings exist —an open-packed, ice-like ring and a closed-packed ring structure. Ficure 4.9 Pauling self-clathrate model for the structure of watet.Chemical Ocean, Fray 130 a vil 2 dis : jw oa . Zl IV ‘00-00 — “Temperature 0) ficune 4.10 hase diagram for the various forms of ice. 4.3.2.2. Cluster Theories Stewart (1931) was the first to suggest the existence of clusters based on his x-ray work. ‘The clusters contained 10,000 water molecules. Nemethy and Scheraga (1962) built on the Frank and Wen (1957) concept of flickering clusters using statistical thermodynamics. They have used this model to calculate the thermodynamic properties of H,O. The authors considered unbonded water molecules and water molecules with 1, 2, 3, and 4 H bonds per molecule. The average cluster varies from 91 to 25 from 0 to 70°C. At 25°C the cluster size is about 50 molecules. Monomeric molecules range from fractions of 0.24 to 0.29 from 0 to 70°C (ie,, 24% of the bonds are broken at 0°C upon melting). Others have made similar calculations by assigning energy bands instead of levels for different states of the H bonding. Only three species are considered: free H,O, one OH group bonded, and two OH groups bonded molecules. They have been able to calculate the thermodynamic properties with great accuracy using these models and formulated models using clusters of H,O molecules of 100 to 700 molecules. 4.3.2.3 Clathrate Cage Models Pauling originally postulated the clathrate cage model. He noted the existence of clathrate hydrates of many inert gases and suggested that water is its own clathrate hydrate. Frank and Quist (1961) developed this model and successfully calculated thermodynamic proP” erties of water in good agreement with experimental values. In the clathrate model discret sites exist in the host lattice (for other H,O molecules or solute molecules). 43.2.4 Significant Structure Theory and Eucken’s Polymer Model ‘The bulky species is ice-like ily like i i Smee eee (pot necessarily like ice 1). The dense species is not necessarily | mon -like species of high« ity. Byri 7 oa lik igher density. E} t all. (1958) v5 signi oat irate theta —aspecific element exists with ea addition ‘omers. Others have extended this treatment by recognizing that the all. Thus, the significant structures are cage ice 1) with in equilibrium an ice [l-like struct, Ae Llike clusters). This model has been u ‘C in density, the vapor pressure, and the 5Tonic Interactions s sv bvaten plies) fae ‘ep (water, 0°O) Log of Time (see) | | 420 46 8 tat 6 Xray Difaction " NMR Chemical Shit —————4 — Sapo Dielectric Relaxation Ligh Scattering Tneate Neutron Setter | ae IR and Raman Spectroscopy Unesonie Absorption ed ——— figure 4.11 Comparison ofthe times of water movernents to the times required to make various measurements. heat (combined with Eyring’s rate theory this model has been used to calculate the pressure dependence of relative viscosity of H,0). Eucken (1949) treated water as a mixture of distinctly associated species of dimers, tetramers, and octamers. Although this method is probably not correct, Wicke (1966) has suggested that dimers may exist near the critical point. Eucken’s theory is interesting in that it is able to estimate thermodynamic properties that agree with the experimental results; however, the model is not correct. It is thus important to note that the fact that a model is able to calculate accurate properties of water does not prove the model is correct. ‘A more critical test of a water theory is its ability to predict correctly, even if only quantitatively, a large variety of widely different properties of water. One of the major difficulties of the mixture models that assume the dense species is monomeric water is in explaining how mere van der Waals forces can provide enough attraction for the single water molecule to avoid escaping into the vapor state. The water molecules in a clathrate cage must also possess some unique properties. It is difficult to see how H,O molecules with their large dipole moment can exist in a clathrate cage with strong interactions. Experimental studies have not proved that H,O molecules reside in clathrate cages. It is important to understand that when we think of the structure of a liquid, it is necessary to consider the timescale used to measure that structure. Depending upon the experimental techniques used (see Figure 4.11), one will take a picture that is related to the shutter speed of the camera. Thermodynamic measurements see an average structure. The time molecules move (ie., the time for molecular displacements) is 10° s in ice and 10""s in the liquid. Recent studies have been made by using techniques that can examine the structure of liquids at very fast rates. These studies are briefly reviewed below. ‘The structure of water outlined above and discussed more recently (Ohmine and Tanaka, 1993) has received some major interest. The debate on the unique structure of water goes ‘on (Soper, 2000; Pratt, 2002). These new studies have used ultrafast probes to study the structure of water. Ruan et al. (2004) have studied thin ice films using laser pulses and measured the structural change by electron diffraction. Their results show a transient structure of water on hydrophobic surfaces. The water molecules at the surface appear to bbe more gas like than in a three-dimensional network. The more recent work of Wernet et al. (2004) indicates that water molecules have only two hydrogen bonds (one a donor and the other an acceptor hydrogen bond). These results do not agree with the earliereee 132 Chemical Oceq ap, y i isi in three or four hydrogen b; that each water molecule is involved in Ben bonds, ee eee molecules in the liquid resemble water on the surface of ice and 80% of the water molecules have only two strong hydrogen bonds on the subfemt (107 sec) timescale, These stronger hydrogen bonds are surrounded by a cluster i hydrogen bonds. The static picture based on x-ray absorption and neutron diffrac integrates the structure of time, giving an average picture of the three-dimensiona] strug. ture in the liquid. ; : These snapshot pictures of liquid water are not consistent with the structure that comes from some earlier molecular dynamics simulations. More recent molecular dynamics studies by Kuo et al. (2004) of the liquid-vapor interface were able to reproduce an} quantify the structure of water on interfaces. Their work supports some recent measure. ments (Du et al,, 1993; Raymond et al., 2003) that provide p roof that water at interfaces has dangling OH bonds, which they call “acceptor-only” hydrogen bonds. These acceptor. only waters are 19%, while the “single-donor” waters are 66% of the waters at the interface. interfaces. For example, the ice. The order of the ions from of I, Br, Cl, F. The most hydrated species is in the bulk water, the behavior of halides at the while I is close to the interf, face. This may be important for interface of aerosols. oa aceasta 4.4 Jon-Water Interactions ‘To understand the behavior of ions in seawater it is important to be able to understand the interactions of ions with water mol i Te aosctlect an initial state devoid of ion-ion interactions. 1 that of ions ina vacuum at an infinitely low pressure (it ice 82s). One considers then the changes in properties such as free ener)’ tok ey AFR, and entropy, AS? for the process denoket by Equation 4.1 called, resp the hydration free ra Bes: enthalpies, and entropies). The methods used to calla ic hydration functions are discussed elsewhere (Robinson and Stok uused to calculate the sed expe” Se ce gan he heat of solution of a given Geen All can be determined ince we L made for the absolute thermody™ il Vit meiner oY the Values for the anther inne can be easi