Topics in Mathematics with Applications to Chemistry Lia Vas

State Functions
A state function is a function of the parameters of the system which only depends upon the parameters values at the endpoints of the path. Thus, the change in a state function is a path independent. For example, the change of temperature is a state function. To illustrate that it is path independent, consider that we can raise the temperature of water for 10 degrees on a few dierent ways: 1) heat the water by 10 degrees, b) heat the water by 100 degrees and wait till it cools down to 10 degrees above the initial temperature, c) stir the water until the temperature gets raised by 10 degrees etc. In thermodynamics, a state function, state quantity, or a function of state, is a property of a system that depends only on the current state of the system, not on the way in which the system got to that state. For example, internal energy, enthalpy and entropy are state quantities. In contrast, mechanical work and heat are process quantities because they describe quantitatively the transition between equilibrium states of thermodynamic systems. When a system changes state continuously, it traces out a path in the state space. The path can be specied by noting the values of the state parameters as the system traces out the path, perhaps as a function of time, or some other external variable. Thus, we can treat state functions as vector functions. Example from Wikipedia: Let us consider the pressure P (t) and the volume V (t) as functions of time from time t0 to t1 . We can now form all sorts of functions of time which we may integrate over the path. For example if we wish to calculate the work done by the system from time t0 to time t1 we calculate state 1 W (t0 , t1 ) = state 0 P dV =
t0 t1

P (t)

dV (t) dt. dt

It is clear that in order to calculate the work W in the above integral, we will have to know the functions P (t) and V (t) at each time t, over the entire path. Thus, the work W is not a state function here. Let us suppose now that we wish to calculate the work plus the integral of V dP over the path. We would have:
t1

(t0 , t1 ) =

P
t0

dV dt + dt

t1

V
t0

dP dt = dt

t1 t0

d(P V ) dt = P (t1 )V (t1 ) P (t0 )V (t0 ). dt

It can be seen that the integrand can be expressed as the exact dierential of the function P (t)V (t) and that therefore, the integral can be expressed as the dierence in the value of P (t)V (t) at the end points of the integration. The product P V is therefore a state function of the system. Thus, in order to determine if a given function is a state function or not, it is key to see when a line integral of a vector function is independent of path.

Plane vector functions. Consider a vector function f = (P, Q). Assume that the derivatives of P and Q are continuous. We shall say that f is conservative vector eld if and only if it is gradient of some scalar function F (t), f = F. In this case, the scalar function F is call a potential function of f . If f = (P, Q), the condition f = F gives us that P = Fx and Q = Fy . Since Fxy = Fyx if F is twice dierentiable function, this gives us that Py = Qx . Conversely, it can be shown that if Py = Qx the vector function is conservative assuming that the domain of f is simply-connected (intuitively, the domain is connected and has no holes). Thus to check if f = (P, Q) is conservative, it is sucient to check if Py = Q x . In addition, let C be a smooth curve r(t) = (x(t), y (t)) with endpoints r(a) = (x(a), y (a)) and r(b) = (x(b), y (b)). Assume that f is dened on a simply-connected region. Then the line integral P dx + Qdy = f (t)dr
C C

is independent of path if and only if f = (P, Q) is conservative (i.e. if Py = Qx ). In this case, if f = F, F dr = F (r(b)) F (r(a)) f (t)dr = P dx + Qdy =
C C C

For a given conservative vector eld (P, Q), a potential function F can be found by integrating P with respect to x and noting that the integration constant has to depend on y. Then dierentiating the result and equating it with Q, we obtain a potential function F. Space vector functions. Consider the vector function f = (P, Q, R). Assume that all the derivatives of P, Q and R are continuous. Similarly as in the two dimensional case, we say that f is conservative vector eld if and only if it is gradient of some scalar function F (t), f = F, called a potential function of f . If f = (P, Q, R), this condition gives us that P = Fx , Q = Fy and R = Fz . Since Fxy = Fyx , Fxz = Fzx , and Fyz = Fzy for F a twice dierentiable function, this gives us that Py = Qx , Pz = Rx and Qz = Ry . Conversely, it can be shown that if these three conditions hold that the vector function is conservative under the assumption that the domain of f is simply-connected. Thus to check if f = (P, Q, R) is conservative, it is sucient to check if Py = Qx , Pz = Rx and Qz = Ry . Let C be a smooth curve r(t) = (x(t), y (t), z (t)) with endpoints r(a) = (x(a), y (a), z (a)) and r(b) = (x(b), y (b), z (b)). Assume that f is dened on a simply-connected region. Then the line integral P dx + Qdy + Rdz = f (t)dr
C C

is independent of path if and only if f = (P, Q, R) is conservative. In this case, if f = F, P dx + Qdy + Rdz =
C C

f (t)dr =
C

F dr = F (r(b)) F (r(a))

The Fundamental Theorem of Calculus. In one-dimensional case, the condition f = F boils down to f = F . Thus the one-dimensional analogue of the formulas for the line integrals above is the well known formula
b b

f (t)dt =
a a

F (t)dt = F (t)|b a = F (b) F (a)

Practice Problems. a) Check if given vector functions are conservative. If they are, nd their potential functions. 1. f = (xey , yex ) 2. f = (x3 y 4 , x4 y 3 + 2y ). b) Find a potential function of given vector functions and use it to evaluate given curve C. 1. f = (x3 y 4 , x4 y 3 ), C is x = t, y = 1 + t3 , 0 t 1. 2. f = (y, x + z, y ), C is the line segment from (2, 1, 4) to (8, 3, 1). 3. f = (2xz + sin y, x cos y, x2 ), C is spiral x = cos t, y = sin t z = t, for 0 t 2. c) Show that the line integral is independent of path and evaluate it. 1. 2.
C C C

f dr along

2x sin ydx + (x2 cos y 3y 2 )dy where C is any path from (-1,0) to (5, 1). ydx + (x + z )dy + ydz where C is any path from (2, 1, 4) to (8, 3, 1).

Solutions. a) 1. Not conservative. 2. Conservative. F = 1 x4 y 4 + y 2 + c. 4

1 4 4 b) 1. F = 4 x y + c, C = F (1, 2) F (0, 1) = 4 0 = 4 2. F = xy + yz + c, 2 = F (8 , 3 , 1) F (2 , 1 , 4) = 21 6 = 15 3. F = x z + x sin y, C = F (1, 0, 2 ) C F (1, 0, 0) = 2 0 = 2.

c) 1. F = x2 sin y y 3 b) 3. C = 15

= F (5, 1) F (1, 0) = 25 sin 1 1 0 = 20.04

2. See part