I have not asked a really embarrassing question in a while, so thought it was time :-). I am stumped as to why the spacing around the = on the third line is incorrect:

Notes:
- I realize I am cheating a bit on the second line, but I don't mind that the equation starts a bit on the left.
- The absolute value is from Absolute Value Symbols, but is not relevant to this problem.
Code:
\documentclass{article}
\usepackage{mathtools}
% https://tex.stackexchange.com/questions/43008/absolute-value-symbols
\DeclarePairedDelimiter\abs{\lvert}{\rvert}%
%% ----- Not relevant for this example
%% Swap the definition of \abs* and \norm, so that \abs
%% and \norm resizes the size of the brackets, and the
%% starred version does not.
%\makeatletter
%\let\oldabs\abs
%\def\abs{@ifstar{\oldabs}{\oldabs}}
\begin{document}
\begin{alignat}{5}
\abs{E_T}
&& {}\le \frac{K (b-a)^3}{12 n^2} &&= 0.005 \
&& \frac{0.2487 (\pi)^3}{12 n^2} &&= 0.005 \
\implies && n^2 &&=128.52 \
&& n &&\approx 11.34
\end{alignat}
\end{document}


\approx, and11.34), just like the first two (=and0.005), so they line up using aright alignment. – Werner Mar 20 '14 at 23:13