First, I don't believe that Secretary of State Rice is next behind Speaker Pelosi. I believe that the President pro tem of the Senate is next in line.
Second, Speaker Pelosi's position in the line of Presidential succession does not make her the "number 3 person" in the government.
Here it is in order:
# Office Officer
1 Vice President and President of the Senate Dick Cheney
2 Speaker of the House of Representatives Nancy Pelosi
3 President pro tempore of the Senate Robert C. Byrd
4 Secretary of State Condoleezza Rice
5 Secretary of the Treasury Henry M. Paulson, Jr.
6 Secretary of Defense Robert Gates
7 Attorney General Alberto Gonzales
8 Secretary of the Interior Dirk Kempthorne
9 Secretary of Agriculture Mike Johanns
-- Secretary of Commerce Carlos Gutierrez
(ineligible; not a natural-born citizen)
-- Secretary of Labor Elaine Chao
(ineligible; not a natural-born citizen)
10 Secretary of Health and Human Services Michael Leavitt
11 Secretary of Housing and Urban Development Alphonso Jackson
12 Secretary of Transportation Mary Peters
13 Secretary of Energy Samuel W. Bodman
14 Secretary of Education Margaret Spellings
15 Secretary of Veterans Affairs Jim Nicholson
16 Secretary of Homeland Security Michael Chertoff