Solving a diffusion-type ODE across a spherical shell, the equation is: $$\frac{d}{dr}\left(r^2\frac{df}{dr}\right)=0\tag{1}$$ with boundary conditions $f(r_1)=f_1$ and $f(r_2)=f_2$.
The solution is: $$f(r)=\frac{f_1-f_2}{\frac{r}{r_1}-\frac{r}{r_2}}+\frac{f_1r_1-f_2r_2}{r_1-r_2}\tag{2}$$ Now I know intuitively that if the overall thickness of the shell $\Delta r=r_2-r_1\ll r_1$, then this can be reduced to Cartesian coordinates. In that case the ODE is: $$\frac{d^2f}{dr^2}=0\tag{3}$$ With the same boundary conditions, then the solution is: $$f(r)=f_1+(f_2-f_1)\frac{r-r_1}{r_2-r_1}\tag{4}$$ All fine so far. What I want to do though is prove that Equation 2 reduces to Equation 4 when $\Delta r\ll r_1$, but I can't seem to figure out how it should be done.
My approach has been to substitute $r_1 + \Delta r$ for $r_2$ and substitute $r_1+\xi$ for $r$, and then use the geometric series $\frac{1}{1-x}\approx 1+x$ (for $x\ll 1$) type of substitution to get $r$ up into the numerator, but the terms don't cancel and I can't get it to work out.
Is there another approach I should be using? Some trick or technique I'm not remembering?
Your idea is correct. As the thickness of the shell diminishes -- the effect of the curvature of the domain becomes negligible. The solution in rectangular coordinates becomes a close approximation to the curvilinear solution.
As you suggested, let $\Delta = r_2 - r_1$ and $\xi = r - r_1$.
The spherical solution is
$$f(r) = \frac{f_2r_2-f_1r_1}{r_2-r_1} + \frac{f_1-f_2}{r(1/r_1 - 1/r_2)}=\frac{f_2(r_1 + \Delta)-f_1r_1}{\Delta} + \frac{f_1-f_2}{\Delta}\frac{r_1(r_1+ \Delta)}{r}\\=f_2(1 + \frac{r_1}{\Delta})-f_1\frac{r_1}{\Delta} + \frac{f_1-f_2}{\Delta}\frac{(r_1+ \Delta)}{1+\frac{\xi}{r_1}}.$$
With $\frac{\xi}{r_1} \ll 1$, we have
$$\frac1{{1+\frac{\xi}{r_1}}} \approx 1 - \frac{\xi}{r_1}.$$
Then
$$f(r) \approx f_2 +\frac{f_2r_1}{\Delta}-\frac{f_1r_1}{\Delta}+ \frac{f_1-f_2}{\Delta}(r_1 + \Delta) + \frac{f_2-f_1}{\Delta}(r_1+\Delta)\frac{\xi}{r_1} \\ = f_1 + \frac{f_2-f_1}{\Delta}\left(1+\frac{\Delta}{r_1}\right)\xi$$
Finally, with $\frac{\Delta}{r_1} \ll 1$ we have
$$f(r) \approx f_1 + \frac{f_2-f_1}{\Delta}\xi= f_1 + \frac{f_2-f_1}{r_2-r_1}(r-r_1)$$