If had to find the rate of change of volume with respect to height given that
and that
at the point where h=2, why does it make a difference if I substitute
first and differentiate the expression and then substitute h=2 in, rather than substituting r for
(the value of r when h is 2) and differentiating that?
As you have

in terms of

, the two are linked, one changes as the other changes according to the relationship you're given. If you differentiate one while you've substituted the other in as a constant, then the second isn't going to change relative to the first, as you've made it constant (think about what happens to

if you just substitute in the constant, is this rate actually representing what is happening?
(no)). So you need to keep everything in terms of everything else, differentiate and apply the chain rule (which is really why you can't just use the constant term first, see what happens here in the two situations), and then substitute in the constants.