Proportionality constants

Diffusivity measures the tendency for a concentration gradient to dissipate to form a molar flux. The proportionality constant between the flux and the potential is called the diffusivity and is expressed in m /s. If a binary mixture of components A and B is considered, the molar flux of component A with respect to a reference plane through which the exchange is equimolar, is expressed as a function of the diffusivity and of the concentration gradient with respect to aji axis Ox perpendicular to the reference plane by the fpllqvving relatipn 6 /... 

Customarily, it is assumed that e is unity and that ]l = p,cos 9, where 0 is the angle of inclination of the dipoles to the normal. Harkins and Fischer [86] point out the empirical nature of this interpretation and prefer to consider only that AV is proportional to the surface concentration F and that the proportionality constant is some quantity characteristic of the film. This was properly cautious as there are many indications that the surface of water is structured and that the structure is altered by the film (see Ref. 37). Accompanying any such structural rearrangement of the substrate at the surface should be a change in its contribution to the surface potential so that AV should not be assigned too literally to the film molecules. 

The existence of this situation (for nonporous solids) explains why the ratio test discussed above and exemplified by the data in Table XVII-3 works so well. Essentially, any isotherm fitting data in the multilayer region must contain a parameter that will be found to be proportional to surface area. In fact, this observation explains the success of Ae point B method (as in Fig. XVII-7) and other single-point methods, since for any P/P value in the characteristic isotherm region, the measured n is related to the surface area of the solid by a proportionality constant that is independent of the nature of the solid. 

In this relationship. S is alkane solubility, A is the cavity surface area and a is the hydrophobic free energy per unit area. Extensive fitting of this equation [24] yields a value of 88 kJ mol A for the proportionality constant a. This value corresponds to an unfavourable free energy of about 3.6 kJ mol for the transfer of a CH2 group to aqueous solution. 

If there are no reactions, the conservation of the total quantity of each species dictates that the time dependence of is given by minus the divergence of the flux ps vs), where (vs) is the drift velocity of the species s. The latter is proportional to the average force acting locally on species s, which is the thermodynamic force, equal to minus the gradient of the thermodynamic potential. In the local coupling approximation the mobility appears as a proportionality constant M. For spontaneous processes near equilibrium it is important that a noise term T] t) is retained [146]. Thus dynamic equations of the form... 

Sensitivity is the change in signal per unit change in the amount of analyte and is equivalent to the proportionality constant, k, in equations 3.1 and 3.2. If ASa is the smallest increment in signal that can be measured, then the smallest difference in the amount of analyte that can be detected is... 

In a rate law, the proportionality constant between a reaction s rate and the concentrations of species affecting the rate k). 

When m = 1.0, as in Fig. 2.5, the exponent becomes zero and the viscosity is independent of 7 when m = 0.7, a factor of 10 change in 7 results in a decrease of viscosity by a factor of 2. This is approximately the case for the data in Fig. 2.5 for 7 values between 10" and 10" sec". Equation (2.14) and its variations are called power laws. Relationships of this sort are valuable empirical tools for extrapolating either F/A or t over modest ranges of 7. In such an application, the exponent m - 1 and the proportionality constant are... 

By analogy with Eq. (3.1), we seek a description for the relationship between stress and strain. The former is the shearing force per unit area, which we symbolize as as in Chap. 2. For shear strain we use the symbol y it is the rate of change of 7 that is involved in the definition of viscosity in Eq. (2.2). As in the analysis of tensile deformation, we write the strain AL/L, but this time AL is in the direction of the force, while L is at right angles to it. These quantities are shown in Fig. 3.6. It is convenient to describe the sample deformation in terms of the angle 6, also shown in Fig. 3.6. For distortion which is independent of time we continue to consider only the equilibrium behavior-stress and strain are proportional with proportionality constant G ... 

Both Eqs. (5.9) and (5.10) predict rate laws which are first order with respect to the concentration of each of the reactive groups the proportionality constant has a different significance in the two cases, however. The observed rate laws which suggest a reactivity that is independent of molecular size and the a priori expectation cited in item (5) regarding the magnitudes of different kinds of k values lend credibility to the version presented as Eq. (5.9). 

Although it is not universally true that the activation energies of reactions parallel their heats of reaction, this is approximately true for the kind of addition reaction we are discussing. Accordingly, we can estimate E = k AH, with k an appropriate proportionality constant. If we consider the difference between two activation energies by combining this idea with Eq. (7.21), the contribution of the nonstabilized reference reaction drops out of Eq. (7.21) and we obtain... 

In writing the second version of this, the proportionality constant has been set equal to unity as a simplification. Note that the resonance stabilization energy of the reference radical Ri- also cancels out of this expression. 

In this expression, called Pick s first law, the proportionality constant D is the diffusion coefficient of the solute. Since J = (l/A)(dQ/dt) and c = Q/V, where Q signifies the quantity of solute in unspecified units, it follows that D has the units length time", or m sec in the SI system. The minus sign in Eq. (9.69)... 

As the attenuation of the incident beam per unit path through the solution, the turbidity is larger than the Rayleigh ratio by the factor Ibrr/S, since T is obtained by integrating Rg over a spherical surface. Thus, if Eq. (10.54) is written in terms of Rg rather than r, the proportionality constant H must also be decreased by l6n/3, in which case the constant is represented by the symbol K ... 

Coulomb s law. This relationship poses no particular difficulties as a qualitative statement the problem arises when we attempt to calculate something with it, since the proportionality constant depends on the choice of units. In the cgs system of units, the electrostatic unit of charge is defined to produce a force of 1 dyne when two such charges are separated by a distance of 1 cm. In the cgs system the proportionality factor in Coulomb s law is unity and is dimensionless. For charges under vacuum we write... 

By contrast, in SI units, the coulomb (C) is the unit of charge and is defined as an ampere second (A sec). To reconcile this with newtons and meters, the units of F and r, respectively, a proportionality constant that is numerically different from unity and which has definite units is required. For charges under vacuum we write... 

The fact that the proportionality constant in Eq. (10.102) is not written as, say, k but also includes the factor (47t)" is a recognition of the fact that 47t arises frequently in equations from geometrical considerations and can be conveniently eliminated by this device. 

Elastic behavior is commonly quantified by the Young s modulus E, the proportionality constant between the appHed tensile stress O, and the tensile strain (A length/original length). 

A general observation, verified for nearly all soHds, is a proportionality between current density and field strength, known as Ohm s law. The electrical conductivity is this proportionality constant and is defined as... 

The H in solubility tables (2-121 to 2-144) is the proportionahty constant for the expression of Henry s law, p = Hx, mere x = mole fraction of the solute in the liqiiid phase p = partial pressure of the solute in the gas phase, expressed in atmospheres and H = a. proportionality constant expressed in units of atmospheres of solute pressure in the gas phase per unit concentration of the solute in the hquid phase. (The unit of concentration of the solute in the liquid phase is moles solute per mole solution.)... 

Diffusion is the molecular transport of mass without flow. The diffu-sivity (D) or diffusion coefficient is the proportionality constant between the diffusion and the concentration gradient causing diffusion. It is usually defined by Fick s first law for one-dimensional, binary component diffusion for molecular transport without turbulence shown by Eq. (2-149)... 

Open-Loop versus Closed-Loop Dynamics It is common in industry to manipulate coolant in a jacketed reacdor in order to control conditions in the reacdor itself. A simplified schematic diagram of such a reactor control system is shown in Fig. 8-2. Assume that the reacdor temperature is adjusted by a controller that increases the coolant flow in proportion to the difference between the desired reactor temperature and the temperature that is measured. The proportionality constant is K. If a small change in the temperature of the inlet stream occurs, then depending on the value or K, one might observe the reactor temperature responses shown in Fig. 8-3. The top plot shows the case for no control (K = 0), which is called the open loop, or the normal dynamic response of the process by itself. As increases, several effects can be noted. First, the reactor temperature responds faster and faster. Second, for the initial increases in K, the maximum deviation in the reactor temperature becomes smaller. Both of these effects are desirable so that disturbances from normal operation have... 

---