The Chemistry Maths Book, Second Edition

(Grace) #1

252 Chapter 9Functions of several variables


and each of these can be differentiated with respect to either variable to give four


partial second derivatives. Differentiation of∂z 2 ∂xgives


and differentiation of∂z 2 ∂ygives


For a function of two variables, there are a possible 8 partial third derivatives, 16


fourth derivatives, and so on; in general a possible 2


n

nth derivatives. In terms of


Figure 9.3, the first derivative∂z 2 ∂xis the gradient at a point, P say, on the curve


APB, and∂


2

z 2 ∂x


2

is the rate of change of this gradient as the point P moves along


the curve. On the other hand, the ‘mixed’ second derivative∂


2

z 2 ∂y∂z 1 = 1 ∂(∂z 2 ∂x) 2 ∂y


is the rate of change of the gradient∂z 2 ∂x(in the x-direction) as the point P moves


along the curve DPE (in the perpendicular y-direction).


We note that, for the cubic function, the two mixed second derivatives are identical.


This is true for functions whose first derivatives are continuous, and is therefore (very


nearly) always true in practice:


(9.6)


Similar results are obtained for higher derivatives.


Alternative notations


The above symbols for partial derivatives become unwieldy for the higher derivatives,


and the following more compact notation is often used:


(9.7)


In this notation, equation (9.6) becomesf


xy

1 = 1 f


yx

and, for example,f


xxy

1 = 1 f


xyx

1 = 1 f


yxx

(subject to the relevant continuity conditions).


In some applications, particularly in thermodynamics, it is necessary to specify


explicitly which variables (or combinations of variables) are to be kept constant. This


is achieved by adding the constant variables as subscripts to the ordinary symbol for the


partial derivative. For example, for a function of three variablesf(x, y, z), the symbol


(9.8)


means the derivative offwith respect to xat constantyandz.


yz


f


x


,










f


f


x


f


f


x


f


f


xy


f


f


xy


x xx xy xyz

=




,=




,=



∂∂


=



∂∂


2

2

23

,


∂∂


,


z


...



∂∂


=



∂∂


22

z


xy


z


yx











=




=+ ,











=



y


z


y


z


y


xy


x


z


y


2

2

624


22

46


z


xy


xy


∂∂


=+











=




=+,











=



x


z


x


z


x


xy


y


z


x


2

2

2

64


zz


yx


xy


∂∂


=+ 46

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