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Silicone rubber does that with age. You can slow down the process by washing the snorkel in fresh water after use and storing it in a cool dark place, but you cannot prevent it.
Spare purge valves simply are not available. Although they are a very cheap item, Aqua Lung (SeaQuest) would rather sell you a complete new snorkel. Most other manufacturers take the same view. It's not entirely unreasonable either: by the time that the valve has hardened, the silicone mouthpiece will be past it's best and the breathing tube itself may have weakened to the point where it will become soft on a hot day and could collapse inwards when you inhale. In addition, the cost of distributing individual purge valves in umpteen different sizes (they are not standardised) would be prohibitive and then the retailer would need to do the same with every brand sold. Each cheap diaphragm would be a lost profit opportunity, and when many dive-shops are already clinging on to survival each sale is a nail in their coffin.
Snorkels are cheap: just buy another is the best option, but if you're a lateral thinker it's usually possible to fabricate your own spare part by cutting it from an old bicycle inner tube or even from balloon rubber; just be careful with how you fasten it as a poor design can result in small parts being inhaled if they break loose.
I use baking soda, warm water and bottle brushes for pretty much anything that goes near my mouth. My hydration bladder gets that treatment often especially after a long trip, as has my snorkel a couple of times. You could try find a platypus or camelbak cleaning kit at your local outdoors store.
From what you've described, you have a self-draining snorkel (at least it would be if working correctly). There will be a simple diaphragm valve at the lowest point of the snorkel, it's usually made of a silicone rubber disc and in use is held closed by external water pressure. It can also be held open if there is any grit or sand in it, if it is damaged or if it's simply hardened with age.
All you can do is clean it and make sure it seats correctly. If it has failed in any way or if the diaphragm is simply missing then buy a new snorkel as they don't need to be expensive.
There's a good reason that many divers still prefer a simple j-tube snorkel and it's because there is nothing to go wrong. I personally do use a self-draining snorkel but I'm careful to inspect and clean the valve before and after every use and always have a spare snorkel in my dive bag.
On an unrelated matter, if the snorkel has any kind of device on the open end to prevent water from entering then I strongly recommend that you remove it. They're restrictive to airflow and are potentially dangerous. There is no substitute for simplicity and for learning to use a snorkel correctly.
Or more to the point: Snorkels don't work under water. They work on the surface by allowing the wearer to have his/her face in the water so that one can look at what is going on and the top of the snorkel is several inches above the surface allowing the user to breath through the tube. If, as often happens, the snorkel gets water in it, there is a trap at the bottom that catches it so you don't **** it into your lungs and on the next exhale you do so forcefully and this expels all the water from the tube and allows you to continue breathing.
Make sure you are gripping the mouthpiece of the snorkel securely with your teeth.
Exhale forcefully through your mouth. The majority of the water should be expelled from the tube. This method is commonly called "blasting" or "popping."
Inhale gently at first in case there is any residual water. Blast a second time if needed.
Continue blasting whenever water enters the snorkel.
"A snorkel must fit comfortably in your mouth, allow you to purge water out of the mouthpiece and hose quickly and help you to swim efficiently. But, the most important characteristics to remember when choosing a snorkel are its length and the diameter of its barrel.
Snorkels must not be too long or too short. If a snorkel is too long it will be difficult to breathe because the barrel will fill up with carbon dioxide. Every time you breathe out carbon dioxide through your snorkel your breath must travel up and out of the barrel of your snorkel to allow you to draw oxygen back down the barrel and into your lungs. If your snorkel is too long you will only push a percentage of the carbon dioxide up and out of the barrel during your exhale. You will need to inhale oxygen before all the carbon dioxide has been pushed out; leaving the percentage of carbon dioxide entering your bloodstream higher each time you take a breath. This cycle could lead to suffocation. If a snorkel is too short it will constantly fill with water, requiring you to constantly force the water out of your snorkel which can be very exhausting.
The inside diameter of your snorkel must be approximately three quarters of an inch or 1.9 cm. If the snorkel is thinner than .75 inches it will be difficult to breathe because there will not be enough room in the barrel for you to draw enough air into your lungs. This will cause you to breathe harder and rapidly, which could cause hyperventilation. If the barrel is thicker than .75 inches it will be too large and will be uncomfortable to use and attach to your mask.
Learning to attach your snorkel to your scuba mask to make sure it is easy to grab and use is an important part of safe scuba diving practices. Snorkels are attached to the left side of your mask with a snorkel keeper. Snorkel keepers are either plastic or rubber and most use a post-hole closure. Each snorkel keeper is different and attaching your snorkel to your mask with a snorkel keeper requires practice. If you will detach your snorkel from your mask after each dive you should practice attaching your snorkel, as it can be a little tricky. Alternately, you can leave your snorkel attached to your mask if you are diving more than once in a day.