I'm not seeing where it was stated that the rectangle is necessarily orthogonal to the axes...
This does appear to be what the OP wrongly assumed:
Two vertices of a rectangle ABCD are A(3,-5) and B(6,-3).
a) Find the gradient of CD.
My working: C is (6,-5) and D is (3,-3). The gradient is -2/3.
b) Find the gradient of BC. I am not sure about this.
The student has likely seen other problems in which this is appropriate reasoning, where the sides
are said to be horizontal and vertical, and it is the
diagonal that is given. So this is probably a case of not seeing what is actually stated, but what one is used to. It looks like a familiar problem, so let's do it that way.
This also requires taking "two vertices" to mean that they are not necessarily
consecutive (and missing the convention for naming polygons consecutively); then it's at least the easiest possibility, and one might not notice that the problem asks about definite facts, not just possibilities. So it's somewhat understandable, though wrong on several counts.
Of course, even interpreting the problem correctly, we have no idea where C and D actually are, which might lead a student away from that interpretation, which seems to have too much uncertainty; in fact, the actual questions asked are just about all that
can be asked.
All of this takes some experience to recognize. A student who is accustomed to fairly basic problems will easily miss the subtle implications that lead to the right interpretation.
Very little was "stated" in the original question (as it was presented) but it is clear (IMNSHO) that this question is intended to test:-
a) the student's knowledge of how to calculate the gradient of a line when two points on it are given (and that the parallel sides of a rectangle share the same gradient)
and
b) the student's knowledge of the relationship between the gradients of perpendicular lines.
Interestingly, although you are probably right about the goal, all sorts of subtleties in
other areas get in the way of seeing it.