If you're an ectomorph then you probably have skinny arms. These are what show when you're wearing a t-shirt, so it's natural that you'd want to work toward bigger arms. That said, I recommend that you follow a full workout plan, but read on if you want to work toward bigger arms.
The arm is made up of two primary muscles - the biceps and the triceps. A lot of people think doing curls is going to make your arms huge. This couldn't be further from the truth. It will help add mass to your arm, but it's important to note that the tricep makes up 2/3 of your arm. It is also the easier muscle to build up. You also have the option of building up your forearm, which'll make the entire mass look bigger - this is even more overlooked than the tricep.
That doesn't mean you should neglect your biceps! In fact, I recommend you work both and do so consistently.
The standard bicep curl is good, but it can be modified to gain even more mass. I suggest doing incline bicep curls, where you sit in an inclined seat and do curls that way. You can also do hammer curls, which is where you hold the dumbbell perpendicular to the ground. These are fantastic because they also heavily work your forearm, so you're hitting both at once. Preacher curls are another great part that'll work the brachialis, which'll make the bridge between your upper arm and forearm larger.
For your triceps I recommend close grip bench press, if you can get the form down. This is a fantastic exercise. What you do is go into the bench and grab the bar with 4-6 inches of space between your hands. Grip the bar tightly and lower it down to your chest - make sure you don't bring it to your stomach. Then push it back up. When you lower the bar you can flare your elbows out slightly. Another good tricep workout are the tricep cable pulldowns. Cable exercises are good because there's always tension on the muscle, which means you're always getting a work out. I'd also recommend skull crushers.
Your forearms will naturally grow in size, but there are a few exercises that can help. The barbell reverse wrist curl is pretty good. You basically sit down and hold onto a barbell and then use your wrists to lift it up. You can find pictures by Googling the term. Another good way to build up your biceps and your forearms is to do chin ups. These are the same as pull ups except your palms face you.
If you do do these exercises then you'll have big arms in no time.
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