This psql session snippet should be self-explanatory:
psql (9.1.7)
Type \"help\" for help.
=> CREATE TABLE languages(language VARCHAR NOT NULL);
CREATE TA
You could define your language column to be of type regconfig which would make your query a bit less verbose i.e.:
CREATE TABLE languages(language regconfig NOT NULL DEFAULT 'english'::regconfig)
I have set english as default above, but that's not required. Afterwards your original query
SELECT language, to_tsvector(language, 'hello world') FROM languages;
would work just fine.