Convert to seconds those strings:
var str1 = '10:20:45';
var str2 = '5:10:10';
str1 = str1.split(':');
str2 = str2.split(':');
totalSeconds1 = parseInt(str1[0] * 3600 + str1[1] * 60 + str1[0]);
totalSeconds2 = parseInt(str2[0] * 3600 + str2[1] * 60 + str2[0]);
// compare them
if (totalSeconds1 > totalSeconds2 ) { // etc...