Even small quantities of water added suddenly to acid of this concentration, will indeed cause the acid to get hot and there is a severe risk of the acid/water mix erupting out of the pipe with predictable consequences. Incidentally, the other missing 5% can be regarded as water in the case of 95% acid, but most manufacturers use a method of manufacturing the acid to this strength which obviates the need to “water-down” 100% acid.
It is not true to state that sulphuric acid liberates hydrogen on contact with metals. Not all metals react with the acid. Furthermore, I think that some posters are recalling their knowledge of the reactivity of metals with dilute sulphuric acid. Concentrated sulphuric acid reactions are often completely different. To complicate matters further, I’d refer readers to any table on the internet showing the Reactivity Series.
By and large, Caustic Soda is indeed safer to use in domestic situations as long as you take common sense precautions and remember that it too is exothermic.