Being an early riser, I usually hit the gym about an hour after a light breakfast. I believe this to be the best time of day for a workout - you are the most rested, and at the peak of your strength, even though it may not feel so.
What you are striving towards is attaining (and keeping) a perfect form, and I believe in quality over quantity, every time. This is why I try to focus on avoiding lifting mistakes, and keeping the quality of my training at its highest.
You should keep your breaks short - 30-45 seconds between sets.
This is my Day 1 workout, targeting my Back, Biceps, Forearms, Abs.
Back Routine
Deadlifts: First 3 sets (15 reps, 12 reps, 10 reps) from the floor and the remaining 3 sets (10 reps, 10 reps, 8 reps) from blocks. Occasionally do a 7th set with 6 reps.
T-Bar Rows: 12 reps, 10 reps, 8 reps using a 7-foot Olympic Bar
Front Pulldowns: 3 sets x 8-10 rep. Stretch the lats between sets.
Dumbbell Row: 3 sets x 8-10 rep. Stretch the lats between sets.
Biceps
One Arm Dumbbell Concentration Curls: 3 sets x 8 -10 reps. Hold the Dumbbell at the top of the movement, squeeze the biceps and lower the dumbbell slowly.
Alternate Dumbbell Curls: 3 sets x 8 -10 reps
45 degree Incline Dumbbell Curls: 12 reps, 10 reps, 8 reps