General Balance Equations

At a school dance, the music begins and hoys and girls pair up to dance. If there are more boys than girls, some boys will be left without partners. The same is true of reactants in a chemical reaction. Rarely in nature are reactants in a chemical reaction present in the exact ratios specified by the balanced equation. Generally, one or more reactants are in excess and the reaction proceeds until all of one reactant is used up. 

Table 6.1 M ass balance equations (general rate model).

Fig. 6.47 Enlarged simulated and measured (sampled) concentration profile in the SMB for fructose-glucose-sucrose (other data see Fig. 6.46).Table 6.1 Mass balance equations (general rate model).

These two mass balance equations generally describe the concentration evolution in the two chambers. Since our purpose of using the diffusion cell to extract useful information about the diffusion, the cell design is usually such that the mass balance equations can be rendered to a simple form for subsequent simpler analysis. With this objective in mind, the chambers volumes can be made small enough such that the gas residence times in the two chambers are much smaller than... 

For ease of exposition, let us limit attention to. two independent reactions--the generalization to more reactions is straightforward. Then the material balance equations take the form... 

Applying tlie generalized form of tlie mass balance Equation 11-56, at constant density, dV/dt = 0. 

The general population balance equation requires numerical methods for its solution and several have been proposed (e.g. Gelbard and Seinfeld, 1978 Hounslow, 1990a,b Hounslow etai, 1988, 1990), of which more later. Fortunately, however, some analytic solutions for simplified cases also exist. 

In principle, given expressions for the crystallization kinetics and solubility of the system, equation 9.1 can be solved (along with its auxiliary equations -Chapter 3) to predict the performance of continuous crystallizers, at either steady- or unsteady-state (Chapter 7). As is evident, however, the general population balance equations are complex and thus numerical methods are required for their general solution. Nevertheless, some useful analytic solutions for design purposes are available for particular cases. 

General Material Balances. According to the law of conservation of mass, the total mass of an isolated system is invariant, even in the presence of chemical reactions. Thus, an overall material balance refers to a mass balance performed on the entire material (or contents) of the system. Instead, if a mass balance is made on any component (chemical compound or atomic species) involved in the process, it is termed a component (or species) material balance. The general mass balance equation has the following form, and it can be applied on any material in any process. 

For any transient process that begins at time t and is terminated at a later time tp, the general integral material balance equation has the form... 

One molecule (or mole) of propane reacts with five molecules (or moles) of oxygen to produce three molecules (or moles) or carbon dioxide and four molecules (or moles) of water. These numbers are called stoichiometric coefficients (v.) of the reaction and are shown below each reactant and product in the equation. In a stoichiometrically balanced equation, the total number of atoms of each constituent element in the reactants must be the same as that in the products. Thus, there are three atoms of C, eight atoms of H, and ten atoms of O on either side of the equation. This indicates that the compositions expressed in gram-atoms of elements remain unaltered during a chemical reaction. This is a consequence of the principle of conservation of mass applied to an isolated reactive system. It is also true that the combined mass of reactants is always equal to the combined mass of products in a chemical reaction, but the same is not generally valid for the total number of moles. To achieve equality on a molar basis, the sum of the stoichiometric coefficients for the reactants must equal the sum of v. for the products. Definitions of certain terms bearing relevance to reactive systems will follow next. 

Every chemical reaction can go in either forward or reverse direction. Reactants can go forward to products, and products can revert to reactants. As you may remember from your general chemistry course, the position of the resulting chemical equilibrium is expressed by an equation in which /Cec], the equilibrium constant, is equal to the product concentrations multiplied together, divided by the reactant concentrations multiplied together, with each concentration raised to the power of its coefficient in the balanced equation. Eor the generalized reaction... 

The heat-balance equation in its general form applicable to any uniformly heated channel ... 

In considering the flow in a pipe, the differential form of the general energy balance equation 2.54 are used, and the friction term 8F will be written in terms of the energy dissipated per unit mass of fluid for flow through a length d/ of pipe. In the first instance, isothermal flow of an ideal gas is considered and the flowrate is expressed as a function of upstream and downstream pressures. Non-isothermal and adiabatic flow are discussed later. 

Balance equations for batch reactors may all be viewed as special cases of the following general equation... 

Application of the general component balance, Equation (1.6), to a steady-state flow system gives... 

For the computation of compressible flow, the pressure-velocity coupling schemes previously described can be extended to pressure-velocity-density coupling schemes. Again, a solution of the linearized, compressible momentum equation obtained with the pressure and density values taken from a previous solver iteration in general does not satisfy the mass balance equation. In order to balance the mass fluxes into each volume element, a pressure, density and velocity correction on top of the old values is computed. Typically, the detailed algorithms for performing this task rely on the same approximations such as the SIMPLE or SIMPLEC schemes outlined in the previous paragraph. 

In electrochemical cells we often find convective transport of reaction components toward (or away from) the electrode surface. In this case the balance equation describing the supply and escape of the components should be written in the general form (1.38). However, this equation needs further explanation. At any current density during current flow, the migration and diffusion fluxes (or field strength and concentration gradients) will spontaneously settle at values such that condition (4.14) is satisfied. The convective flux, on the other hand, depends on the arbitrary values selected for the flow velocity v and for the component concentrations (i.e., is determined by factors independent of the values selected for the current density). Hence, in the balance equation (1.38), it is not the total convective flux that should appear, only the part that corresponds to the true consumption of reactants from the flux or true product release into the flux. This fraction is defined as tfie difference between the fluxes away from and to the electrode ... 

Generally, the temperature changes with time or, equivalently, with distance from the reactor inlet (for flow reactors). This change is usually controlled well in reaction calorimeters but can become uncontrolled in other conventional laboratory flow or (semi)batch reactors. The balance equations of a batch reactor for a single reaction of a-th order kinetics are given by ... 

Momentum balance equations are of importance in problems involving the flow of fluids. Momentum is defined as the product of mass and velocity and as stated by Newton s second law of motion, force which is defined as mass times acceleration is also equal to the rate of change of momentum. The general balance equation for momentum transfer is expressed by... 

It becomes necessary to incorporate a total mass balance equation into the reactor model, whenever the total quantity of material in the reactor varies, as in the cases of semi-continuous or semi-batch operation or where volume changes occur, owing to density changes in flow systems. Otherwise the total mass balance equation can generally be neglected. 

An alternative approach to the solution of the system dynamic equations, is by the natural cause and effect mass transfer process as formulated, within the individual phase balance equations. This follows the general approach, favoured by Franks (1967), since the extractor is now no longer constrained to operate at equilibrium conditions, but achieves this eventual state as a natural consequence of the relative effects of solute accumulation, solute flow in, solute flow out and mass transfer dynamics. 

Ca ], can be balanced using the general macroscopic population balance equation as follows... 

Let Fn be the total flow in stream n, and xn m the concentration of component m in stream n. Then the general balance equation can be written... 

All the examples of energy balances considered previously have been for steady-state processes where the rate of energy generation or consumption did not vary with time and the accumulation term in the general energy balance equation was taken as zero. 

This procedure for deriving the set of material balance equations is quite general. For a process with n units there will be a set of n equations for each component. 

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