The expected number of comparisons is sum_{i=1...n}(i * p_i).
Re-ordering the elements in descending order reduces the expectation. That's intuitive since by looking at the most probable choices first will reduce, on average, the number of elements looked at before you find a particular choice.
As an example, suppose there's three items k1, k2, k3 with match probabilities 10%, 30% and 60%.
Then in the order k1, k2, k3, the expected number of comparisons is 1*0.1 + 2*0.3 + 3*0.6 = 2.5
With the most likely first: k3, k2, k1, the expected number of comparisons is 1*0.6 + 2*0.3 + 3*0.1 = 1.5