One way in particular is how we refer to the day, and when is an acceptable to time to call, or expect to be able to make an appointment.
I was recently trying to make an appointment and the gentleman told me the day of week he was available, and in the afternoon. Great I thought, and suggested 2pm. He chuckled a little and let me know 4:30 was the earliest he could make an afternoon appointment.
Times of the day have different words and meanings.
For example:
the early morning hours, say 1am - 5 am - here they are called madrugada - this is about the time parties start to wind down and people start to head home.
Morning - from say 7am to noon is matutina or en la manana,
Mid Day - medio dia is from say noon to 3/4, this when it is really tough to make appointments. People go to lunch from say 1:30 - 3:30.
Afternoon - from 4ish to 7ish is vespertina or en la tarde - this is a great time to do appointments.
Evening - 8pm till 1am would be noche. This is when people start to get moving for dinners out, dinners with friends, parties etc. Although few would ever get anywhere at 8pm. If you tell someone 8pm, expect them about 9:30. We were once accused of having a kid party when we told a mexican friend our party started at 8pm.
Don't call people before 9am, 10 is better. But you can call them up to 10pm, even later if you know them.
If you want to meet for lunch, 2:30-3pm is correct. So forget about an appointment with anyone because they are out to lunch. Anywhere between 2 and 5 is sort of a quiet zone, People are either eating, resting, or handling personal business.
It takes a bit to get used to, but what a difference it will make if you get accustomed to these general ideas.